CN106575769A - Secondary battery negative electrode resin composition, method for producing secondary battery negative electrode carbon material, secondary battery negative electrode carbon material, modified phenolic hydroxyl group for use in secondary battery negative electrode, secondary battery negative electrode active material, secondary battery negative electrode, and secondary battery - Google Patents

Secondary battery negative electrode resin composition, method for producing secondary battery negative electrode carbon material, secondary battery negative electrode carbon material, modified phenolic hydroxyl group for use in secondary battery negative electrode, secondary battery negative electrode active material, secondary battery negative electrode, and secondary battery Download PDF

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Publication number
CN106575769A
CN106575769A CN201580044501.2A CN201580044501A CN106575769A CN 106575769 A CN106575769 A CN 106575769A CN 201580044501 A CN201580044501 A CN 201580044501A CN 106575769 A CN106575769 A CN 106575769A
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China
Prior art keywords
secondary battery
negative pole
battery negative
carbon
carbon element
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Inventor
东崎荣造
三井保明
伊东寿
炭山宜也
小林义和
小野哲志
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Sumitomo Bakelite Co Ltd
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Sumitomo Bakelite Co Ltd
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Priority claimed from JP2015100464A external-priority patent/JP2016164861A/en
Priority claimed from JP2015100465A external-priority patent/JP2016164862A/en
Application filed by Sumitomo Bakelite Co Ltd filed Critical Sumitomo Bakelite Co Ltd
Priority claimed from PCT/JP2015/073999 external-priority patent/WO2016031854A1/en
Publication of CN106575769A publication Critical patent/CN106575769A/en
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/446—Initial charging measures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/78—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by stacking-plane distances or stacking sequences
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides a secondary battery negative electrode resin composition containing a phenolic hydroxyl group-containing resin, the hydroxyl group equivalent of which is no more than a prescribed value. A secondary battery negative electrode resin composition according to an embodiment of the present invention contains a phenolic hydroxyl group-containing resin, the hydroxyl group equivalent of which is no more than 300g/eq, and a phosphoric acid ester or phosphoric acid derivative, the boiling point or pyrolysis temperature of which exceeds the self-condensation temperature of the phenolic hydroxyl group-containing resin.

Description

The manufacture of secondary battery negative pole resin combination, secondary battery negative pole material with carbon element Method, secondary battery negative pole material with carbon element, the secondary battery negative pole hydroxyl containing phenol that is modified The resin of base, secondary battery negative pole active substance, secondary battery negative pole and secondary Battery
Technical field
The present invention relates to a kind of secondary battery negative pole resin combination, the manufacturer of secondary battery negative pole material with carbon element Method, secondary battery negative pole material with carbon element, the secondary battery negative pole modified resin containing phenolic hydroxyl group, secondary battery negative pole activity Material, secondary battery negative pole and secondary cell.
Japanese patent application 2014-176596 that the application is filed an application based on August in 2014 29 days in Japan, 2014 Japanese patent application 2014-176597 that on August 29, is filed an application in Japan, August in 2014 propose Shen on 29th in Japan Japanese patent application 2014-176598 please, the Japanese patent application 2015- for filing an application in Japan for 27 days 2 months for 2015 No. 039364, the Japanese patent application 2015-039365 filed an application in Japan on 2 27th, 2015, on 2 27th, 2015 The Japan that the Japanese patent application 2015-039366 filed an application in Japan, on May 15th, 2015 are filed an application in Japan is specially Profit application 2015-100463, the Japanese patent application 2015-100464 filed an application in Japan of on May 15th, 2015 and The Japanese patent application 2015-100465 CLAIM OF PRIORITYs that on May 15th, 2015 files an application in Japan, and its content is helped With into the application.
Background technology
In recent years, in the various technical fields of the big machinery product such as from the small-sized electric product such as portable phone to automobile In studying the utilization of secondary cell.As secondary cell, studying using organic bath etc. as the non-of electrolyte Water electrolysis liquid secondary battery or using solid electrolyte as electrolyte all kinds such as solid state battery.Any type of two In primary cell, by becoming the chemical species (such as lithium ion etc.) of the carrier of secondary cell in the electrode activity of positive pole Move and charging and discharging is repeated in material layer and the electrode active material layer of negative pole.
Generally in the secondary cell, it is arranged in the electrode active material layer of negative pole containing material with carbon element as electrode activity Material.Above-mentioned electrode active material layer and is released in the interlayer occlusion chemical species of the material with carbon element as Rotating fields from the interlayer Release the above-mentioned chemical species or active substance of institute's occlusion, the charging and discharging thus, it is possible to realize secondary cell.
As above-mentioned material with carbon element, the material with carbon element using oil as initial substance was widely used in the past.For example in patent documentation 1 Disclose and possess the negative electrode active material of the amorphous carbon including graphite and containing phosphorus, oxygen and irreversible impurity (hereinafter also referred to Prior art 1) negative electrode for lithium secondary battery.Specifically, prior art 1 illustrate containing following negative electrode active material into Situation about dividing：The negative electrode active material composition is existed by will add material obtained from phosphorus-containing compound in raw petroleum coke charcoal Heat at 500～1500 DEG C and form amorphous carbon, and add graphite wherein and mixed and formed.In patent documentation 1 Illustrate, the discharge and recharge effect of the admixed graphite in the prior art 1 as amorphous carbon and the negative pole active substance that formed Fruit is high.
Illustrate in patent documentation 1, make the reason for containing phosphorus in negative electrode active material composition be to increase lithium ion Hold-up.Speculate in patent documentation 1, by the way that easily negatively charged phosphorus is added into negative electrode active material composition, in Jiao Multiple donor sites are formed in charcoal, it becomes the adsorption site of lithium ion.In patent documentation 1, as the concrete example of phosphorus, enumerate Phosphorus pentoxide, phosphoric acid, phosphate.
On the other hand, be also carried out it is some it is different from above-mentioned prior art 1, using the material beyond oil as initial substance Material with carbon element research.For example Patent Document 2 discloses and organic material is carbonized and is formed and comprising containing prescribed limit amount Phosphorus carbonaceous material negative electrode battery (hereinafter also referred to prior art 2).In patent documentation 2, as in prior art 2 Becoming the organic material illustration of initiation material has phenolic resin.
Specifically, in the embodiment 2 of patent documentation 2, by adding phosphoric acid to novolak phenolics powder Aqueous solution etc. is simultaneously burnt till, and the carbonaceous material containing phosphorus is generated, so as to make the prior art 2 for possessing it.
In the same manner as patent documentation 1, also have in patent documentation 2 as described below：Contain phosphorus by making prior art 2, increasing Big carbonaceous material is highly effective relative to the aspect of the doping of lithium.In addition, illustrating to patent documentation 3 below.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Publication 10-241690 publication
Patent documentation 2：Japanese Unexamined Patent Publication 3-137010 publication
Patent documentation 3：Japanese Unexamined Patent Publication 10-223226 publication
The content of the invention
The invention technical task to be solved
Phenolic resin be can synthetic material, the used diversified secondary cell of technical field can be corresponded to, expand The degree of freedom of exhibition negative pole design, therefore expected as the initial substance of the material with carbon element in negative pole.
Present inventors studied by phenolic resin with novolak phenolics as representative, molecular structure is simplified And the phenolic resin being readily synthesized is used as the initial substance for generating secondary battery negative pole material with carbon element.
Learnt according to the research of the present inventor, be simplified using molecular structure and phenolic resin that hydroxyl equivalent is little generates The charging capacity and efficiency for charge-discharge of material with carbon element also has room for improvement.Above-mentioned problem is not only the problem of phenolic resin, and And be the common problem of the resin containing phenolic hydroxyl group comprising m-cresol resin or naphthol resin etc..
The present invention be in view of above-mentioned problem and complete.That is, the present invention is in view of be advantageously used hydroxyl equivalent for regulation Initial substance of the following resin containing phenolic hydroxyl group of value as secondary battery negative pole material with carbon element, there is provided one kind contains phenol containing this The secondary battery negative pole of the resin of property hydroxyl is with resin combination (hereinafter also referred to as resin combination).
Also, the present invention provides a kind of manufacture method of the secondary battery negative pole material with carbon element using above-mentioned resin combination (hereinafter also referred to as material with carbon element manufacture method).
Also, the present invention provides a kind of secondary battery negative pole manufactured using above-mentioned resin combination with material with carbon element (below Also referred to as material with carbon element).
Also, the present invention provides a kind of secondary battery negative pole generated containing above-mentioned secondary battery negative pole material with carbon element and uses Active substance, the secondary battery negative pole constituted with active substance using the secondary battery negative pole and using the secondary battery negative pole Secondary cell.
Also, the present inventor with the initial substance of material with carbon element as secondary battery negative pole by the use of phenolic resin in order to be carried out Further investigation.As a result, learn, although the novolak phenolics molecular structure that prior art 2 is used is simplified And be readily synthesized, but be difficult to show sufficient battery performance using its material with carbon element generated as initial substance.It is more specific and Speech, learns possess the electricity containing the material with carbon element generated using novolak phenolics as initial substance and by previous methods The efficiency for charge-discharge of the negative pole of pole active material layer is simultaneously insufficient.
The present invention be in view of above-mentioned problem and complete.That is, problem of the invention is to provide one kind to can help to improve The modified resin containing phenolic hydroxyl group of the efficiency for charge-discharge of secondary battery negative pole.
More specifically, the present invention is in view of above-mentioned problem, and providing a kind of can generation can improve the two of efficiency for charge-discharge The secondary battery negative pole of the primary cell carbon material used as anode resin containing phenolic hydroxyl group that is modified.
Also, the present invention provides a kind of secondary battery negative pole carbon generated using the above-mentioned modified resin containing phenolic hydroxyl group Material.
Also, the present invention provides a kind of secondary battery negative pole active substance containing above-mentioned material with carbon element, possesses containing above-mentioned The secondary battery negative pole of the secondary battery negative pole active material layer of negative electrode active material and the secondary cell for possessing above-mentioned negative pole.
Also, the result that the present inventor is studied, it is thus identified that：As patent documentation 1 and 2 is implied, by making two Material with carbon element contained by primary cell negative pole active substance contains phosphorus, and the lithium ion hold-up of the material with carbon element is in the trend of increase. It is preferred at the aspect of the electric capacity increase of the increase because of the lithium ion hold-up and negative pole.
However, the battery performance in order to reliably improve secondary battery negative pole, the hold-up for only increasing lithium ion does not fill Point, it is necessary to also increase the burst size of the lithium ion of release institute occlusion while the hold-up of lithium ion is increased.
From from the viewpoint of release lithium ion, prior art 2 also has room for improvement.
Also, with regard to same viewpoint, record in patent documentation 1, by being given birth to using graphite in the lump with prior art 1 Into negative pole active substance, it is possible to decrease the irreversible capacity of negative pole active substance.That is, illustrate have in patent documentation 1, by with In the lump the irreversible capacity containing lithium ion constitutes negative pole active substance to prior art 1 less than the graphite of amorphous carbon, makes The effect of the irreversible capacity for reducing secondary battery negative pole can have been given play to it.
However, with prior art 1 in the lump admixed graphite and make the negative pole that the irreversible capacity of lithium ion is lowered and live Property material, does not improve completely the irreversible capacity of the lithium ion of of prior art 1 itself.In order to improve the burst size of lithium ion and with The degree of freedom of the design for making that negative pole active substance can be limited in negative pole active substance as requirement containing graphite, therefore It is not preferred.Therefore, from from the viewpoint of the release (that is, the reduction of the irreversible capacity of lithium ion) of the lithium of of prior art 1 itself, Prior art 1 also also has room for improvement.
The present invention be in view of above-mentioned problem and complete.That is, the present invention provides a kind of occlusion of the chemical species such as lithium ion Amount and the improved secondary battery negative pole material with carbon element of burst size.
Also, the present invention provides a kind of secondary battery negative pole generated containing above-mentioned secondary battery negative pole material with carbon element and uses Active substance, the secondary battery negative pole constituted with active substance using the secondary battery negative pole and using the secondary battery negative pole Secondary cell.
For solving the means of technical task
The secondary battery negative pole of one mode of the present invention is contained with resin combination：Hydroxyl equivalent is below 300g/eq The resin containing phenolic hydroxyl group；Temperature is self condensed with boiling temperature or heat decomposition temperature more than the above-mentioned resin containing phenolic hydroxyl group Phosphate ester or phosphoric acid derivatives.
Also, the manufacture method of the secondary battery negative pole material with carbon element of a mode of the present invention is two using the present invention The manufacture method of the secondary battery negative pole material with carbon element of primary cell negative pole resin combination, it is characterised in that have：First burns Into operation, firing condition of maximum temperature during burning till less than 1000 DEG C is entered to above-mentioned secondary battery negative pole with resin combination Row burns till and generates material with carbon element precursor；With the second firing process, maximum temperature during burning till is more than 1000 DEG C of temperature Firing condition burns till to the above-mentioned material with carbon element precursor generated in above-mentioned first firing process, thus generates material with carbon element.
Also, the secondary battery negative pole material with carbon element of a mode of the present invention is the secondary battery negative pole using the present invention The secondary battery negative pole material with carbon element manufactured with resin combination, it is characterised in that the particle diameter distribution containing with good grounds number benchmark The surface area of the per unit volume obtained is 10000cm-1Above 16000cm-1The carbon granule of following scope.
Also, the secondary battery negative pole of the present invention feature of active substance (hereinafter also referred to as negative pole active substance) It is, the secondary battery negative pole material with carbon element containing the present invention.
Also, the secondary battery negative pole (hereinafter also referred to as negative pole) of the present invention is characterised by having：Containing the present invention Secondary battery negative pole active substance secondary battery negative pole active material layer；Use with above-mentioned secondary battery negative pole is laminated with The negative pole collector of active material layer.
Also, the secondary cell of the present invention is characterised by, possess secondary battery negative pole, the electrolyte and secondary of the present invention Anode.
Also, the secondary battery negative pole of a mode of the present invention is characterised by with the modified resin containing phenolic hydroxyl group, Hydroxyl equivalent is more than 115g/eq.
Also, the secondary battery negative pole material with carbon element of a mode of the present invention is characterised by, it is using the present invention Secondary battery negative pole generated with the modified resin containing phenolic hydroxyl group.
Also, the secondary battery negative pole of a mode of the present invention feature of material with carbon element (hereinafter also referred to as material with carbon element) It is, using carbon as main component, phosphorus to be contained with the scope below more than 0.3 mass % 1.5 mass %, and carbon dioxide Adsorbance is less than per unit weight 10ml/g.
Invention effect
Resin combination of the invention, it is possible to provide it is a kind of with hydroxyl equivalent as setting below containing phenolic hydroxyl group Resin as secondary battery negative pole material with carbon element initial substance, charging capacity and efficiency for charge-discharge is compared with the past is improved Negative pole.
Also, material with carbon element manufacture method of the invention, can manufacture it is a kind of with hydroxyl equivalent as setting below contain The resin of phenolic hydroxyl group as initial substance, the improved material with carbon element of battery behavior.
Also, the material with carbon element of the present invention can provide a kind of negative pole, the negative pole be charging capacity and efficiency for charge-discharge with it is conventional Compare improved negative pole, even and if at low ambient temperatures the increase of resistance be also suppressed.
The negative pole active substance of the present invention makes the charging capacity and efficiency for charge-discharge of the negative pole for possessing it compared with the past Improved.Also, by the material with carbon element containing the present invention, even if the negative pole of present invention active substance provides one kind in low temperature The negative pole that the increase of resistance is also suppressed under environment.
Therefore, negative pole of the invention and to possess its secondary cell charging capacity and efficiency for charge-discharge under normal temperature environment excellent It is different.Also, from from the viewpoint of using above-mentioned material with carbon element, even if the present invention negative pole and possess its secondary cell in low temperature ring Also high battery performance can be played under border.
The modified resin containing phenolic hydroxyl group of the present invention is favorably improved the efficiency for charge-discharge of secondary battery negative pole.That is, with The phenolic resin that the molecular structure using as novolak phenolics is simplified is compared as the situation of initial substance, with In the case that the modified resin containing phenolic hydroxyl group of the present invention is as initial substance, can improve and possess the material with carbon element that is generated by it The efficiency for charge-discharge of negative pole.
Also, the material with carbon element of the present invention and the negative electrode active material containing the material with carbon element are favorably improved secondary battery negative pole Efficiency for charge-discharge.
Therefore, the efficiency for charge-discharge of negative pole of the invention is excellent, and the secondary cell of the invention for possessing the negative pole shows Excellent battery performance.
The phosphorus that the material with carbon element of one mode of the present invention passes through the amount containing prescribed limit, and the adsorbance of carbon dioxide Below prescribed limit, the hold-up and burst size of the chemical species such as lithium ion are improved.
Also, containing the present invention material with carbon element negative pole active substance can improve the negative pole for possessing it charging capacity and Efficiency for charge-discharge.
Therefore, the charging capacity and efficiency for charge-discharge of negative pole of the invention are excellent, possess the of the invention secondary of the negative pole Battery shows excellent battery performance.
Description of the drawings
Fig. 1 is of the lithium rechargeable battery for representing the material with carbon element generated containing the resin combination using the present invention The schematic diagram of example, be also as the present invention secondary cell an example lithium rechargeable battery schematic diagram, be also Expression possesses the schematic diagram of an example of the lithium rechargeable battery of the negative pole using the material with carbon element manufacture of the present invention.
Specific embodiment
First, the 1st aspect of the present invention is illustrated.
The present invention can be used in the resin containing phenolic hydroxyl group with novolak phenolics or naphthol resin etc. well It is the molecular structure simply resin containing phenolic hydroxyl group that represents as generating the starting of secondary battery negative pole material with carbon element Material.The molecular structure simply resin containing phenolic hydroxyl group refers to the little resin containing phenolic hydroxyl group of hydroxyl equivalent in general, Specifically, hydroxyl equivalent is below 300g/eq.
So generating secondary battery negative pole carbon materials less than the resin containing phenolic hydroxyl group of setting using hydroxyl equivalent In the case of material (hereinafter also referred to as material with carbon element), it is difficult to obtain sufficient battery behavior in the past.The present inventor speculates its reason It is as follows.I.e., thus it is speculated that for by the firing process of the resin carbonation containing phenolic hydroxyl group, the resin for containing phenolic hydroxyl group to be possessed At least a portion of hydroxyl be crosslinked in intramolecular and/or intermolecular dehydrating condensation.Think because the crosslinking causes material with carbon element The growth of the crystal structure in firing process is hindered, it is difficult to form the micro- of the preferred carbon containing class graphene-structured It is brilliant.As a result, speculating the occlusion releasability of the chemical species such as the lithium ion of the material with carbon element and insufficient, it is difficult to play excellent Charging capacity and efficiency for charge-discharge.The maximum set body that can be considered monocrystalline is referred in this crystallite.
In contrast, the hydroxyl equivalent of the resin containing phenolic hydroxyl group contained by the resin combination of the present invention is 300g/ Below eq, and exceed the phosphate ester for self condensing temperature of the resin containing phenolic hydroxyl group containing boiling temperature or heat decomposition temperature Or phosphoric acid derivatives (hereinafter also referred to phosphate ester etc.).Thus can provide charging capacity and efficiency for charge-discharge excellent material with carbon element.
By exceeding containing phenolic hydroxyl group containing boiling temperature or heat decomposition temperature in resin combination in the present invention Phosphate ester for self condensing temperature of resin etc., the reason for the battery behavior of the material with carbon element generated using the resin combination is improved not Clearly.But speculate that the reason is as follows.That is, the present inventor speculates, is being burnt in order to the resin combination of the present invention is carbonized Into in the case of, in the resin containing phenolic hydroxyl group the moment (hydroxyl that i.e. resin containing phenolic hydroxyl group possesses for self condensing is started Carry out dehydrating condensation and in intramolecular and/or the intermolecular stage for crosslinking reaction), exist in reaction system not boiling or Undecomposed phosphate ester etc..Therefore, phosphate ester etc. carries out hydrogen bonding etc. or is covered with the hydroxyl of the resin containing phenolic hydroxyl group, Thus the reactivity of the hydroxyl is reduced, suppresses the crosslinking caused by dehydrating condensation, so as to avoid the growth of crystal structure of carbon from receiving To situation about hindering.In the present invention, as long as no special instructions, the phenol for referring to that the resin containing phenolic hydroxyl group has is self condensed Hydroxyl is in intramolecular and/or intermolecular carries out dehydrating condensation.
The present inventor is under X-ray diffraction to using containing novolak phenolics and phosphorus source (specifically phosphorus The phosphate esters such as triphenyl phosphate ester (triphenyl phosphate)) resin combination sample 1 generate material with carbon element crystal structure It is measured, results verification significantly shows near 25 ° of the angle of diffraction (2 θ/deg CuK α) presence of graphene-structured. On the other hand, the resin combination for being prepared using same with above-mentioned resin combination sample 1 mode in addition to without phosphorus source Thing sample 2 similarly carries out X-ray diffraction, does not as a result observe as resin combination sample 1 near 25 ° of the angle of diffraction The notable presence of graphene-structured.
For example, the phosphorus compound of the low-molecular-weight described in patent documentation 1 or 2, normally boiling temperature and heat decomposition temperature Temperature is self condensed less than phenolic resin.Result, it is believed that in order to by the phosphorus compound containing phenolic resin and low-molecular-weight Resin combination be carbonized and in the case of being burnt till, the molecular structure of phosphorus compound decomposed when phenolic resin is self condensed or At least a portion disappears.Therefore, in the resin combination containing phenolic resin and the phosphorus compound of low-molecular-weight, inhibition of sintering Into when the effect of crosslinking that caused by the dehydrating condensation of the hydroxyl of phenolic resin and insufficient.
In addition, in this manual, " class graphene-structured " refers to the structure for being at least partially following structure：Have The chip architecture of the structure same or like with the carbon hexagonal mesh structure shown in Graphene or the chip architecture are laminated and obtain The stepped construction for arriving.Also, in this manual, electrode active material refer to can occlusion and release become the chemicals of carrier The material planted.Above-mentioned chemical species can enumerate lithium ion or sodium ion etc. for example in alkali metal ion secondary cell.
<Secondary battery negative pole resin combination>
Hereinafter, the mode of the resin combination to being used to implement the present invention is described in detail.
The secondary battery negative pole of present embodiment is contained with resin combination：Hydroxyl equivalent is below 300g/eq containing phenol The resin of property hydroxyl；With the phosphoric acid for self condensing temperature that boiling temperature or heat decomposition temperature exceed the above-mentioned resin containing phenolic hydroxyl group Ester or phosphoric acid derivatives.
The charging capacity and efficiency for charge-discharge of the material with carbon element generated using the resin combination of present embodiment is improved, Battery behavior is excellent.By the way that charging capacity is improved in the lump with efficiency for charge-discharge, can substantially improve and use present embodiment Resin combination generate material with carbon element battery behavior.
By above-mentioned composition, the phenomenon of the boilings such as phosphate ester can be suppressed before the resin containing phenolic hydroxyl group is self condensed With thermal decomposition phenomenon in it is at least any of.In the present embodiment, it is more preferably super using boiling temperature and heat decomposition temperature Cross the phosphate ester or phosphoric acid derivatives that self condense temperature of the resin containing phenolic hydroxyl group.
In the present embodiment, the resin containing phenolic hydroxyl group refers to that intramolecular has the resin of phenolic hydroxyl group.This embodiment party The resin containing phenolic hydroxyl group in formula is included：Novolak phenolics or resol type phenol resin (resol-type Phenolic resin) etc. the resin that synthesized as initial substance using phenol；M-cresol resin, xylenol resin, naphthols The resin that resin etc. is synthesized using the phenols beyond phenol；Beyond in the presence of the catalyst of acid or alkalescence by phenol The intramolecular that the aldehydes such as monomer and formaldehyde synthesizes and formed has the resin of phenolic hydroxyl group；Or make to contain modifying agent in above-mentioned resin And the modified resin containing phenolic hydroxyl group for being formed.
For example, the above-mentioned compound containing phenolic hydroxyl group can be closed by making phenols be reacted with any compound of reaction Into.
In this manual, novolak phenolics refer to make under an acid catalysis above-mentioned phenols and formaldehyde react and The phenolic resin of synthesis.Also, in this manual, resol type phenol resin is referred to makes above-mentioned phenols and first under base catalyst Aldehyde reaction and the phenolic resin that synthesizes.
Catalyst can be as needed used in the synthesis of the resin containing phenolic hydroxyl group.
The organic compound with hydroxyl in this phenols refers to aromatic compound, not only comprising so-called phenol, and And the organic compound of the functional group beyond 1 hydroxyl is provided with phenyl ring comprising cresol etc..Above-mentioned compound of reaction is not only Comprising formaldehyde, and comprising can synthesis modification containing phenolic hydroxyl group resin modifier compound.
As the concrete example of phenols, for example, can enumerate：Phenol；Orthoresol, metacresol, paracresol, xylenols or to uncle The alkyl substituted benzene phenols such as butylphenol；The aromatic series substituted benzene phenols such as 4-hydroxydiphenyl；Catechol or resorcinol etc. two First phenol；Aphthols such as alpha-Naphthol or betanaphthol etc., but it is not limited to this.
In the present embodiment, hydroxyl equivalent refers to molecular weight of the resin containing phenolic hydroxyl group relative to 1 hydroxyl.Hydroxyl The measure of equivalent can be carried out according to the neutralization titration of the defineds of JIS K 0070 (1992).
Generally, hydroxyl equivalent it is less (for example hydroxyl equivalent be below 200g/eq, be further below 150g/eq, especially For below 120g/eq), it is more preferred from from the viewpoint of ease of manufacturing and manufacturing cost, more expect as secondary battery negative pole With the use of material.The little resin containing phenolic hydroxyl group of such hydroxyl equivalent, by containing the resin combination in the present invention In, substantially can be used as to provide the initial substance of the material with carbon element for showing excellent battery behavior.
Phosphate ester used in present embodiment etc. shows that than above-mentioned hydroxyl equivalent be below 300g/eq containing phenol The resin of hydroxyl self condenses the high boiling temperature of temperature or heat decomposition temperature.
The temperature that self condenses of resin of the here containing phenolic hydroxyl group is referred in resin of the heating containing phenolic hydroxyl group, at this containing phenol Any part of the multiple hydroxyls contained by the resin of property hydroxyl is in intramolecular and/or the temperature of intermolecular generation dehydrating condensation Refer to the temperature during endothermic reaction that the resin containing phenolic hydroxyl group is carried out means of differential scanning calorimetry measure and shown near 300 DEG C Degree.For example, the hydroxyl equivalent with novolak phenolics as representative as prescribed limit below the resin containing phenolic hydroxyl group The dehydration condensation including hydroxyl self condense temperature for 300 DEG C or so (such as less than more than 300 DEG C 350 DEG C of models Enclose).
Phosphate ester in present embodiment, be with phosphoric acid in part or all of 3 hydrogen be substituted by organic group Structure, and boiling temperature or heat decomposition temperature exceed the resin containing phenolic hydroxyl group contained by resin combination self condense temperature Organic phosphorus compound.
As the example of phosphate ester, following such compound can be enumerated.But following illustration is not to the present invention It is limited in any way.
As phosphate ester, specifically, can illustrate：Triphenyl phosphate (such as Daihachi Chemical Industry Co., Ltd. (DAIHACHI CHEMICAL INDUSTRY CO., LTD.) is manufactured, fire retardant, non-halogen phosphoric acid ester, trade name：TPP), phosphoric acid Cresol diphenyl ester (such as Daihachi Chemical Industry Co., Ltd.'s manufacture, fire retardant, non-halogen phosphoric acid ester, trade name：CDP), phosphoric acid first Phenol two (2,6- xylyl) ester (such as Daihachi Chemical Industry Co., Ltd.'s manufacture, fire retardant, non-halogen phosphoric acid ester, trade name： PX-110), fire retardant " trade name manufactured as Daihachi Chemical Industry Co., Ltd. without halogen system phosphate ester of commercially available product： DAIGUARD-1000”.The phosphate ester that above-mentioned illustration is enumerated is phosphotriester.
Also, phosphate ester is alternatively condensed phosphoric acid esters, for example can be exemplified as the aromatic condensation phosphate ester of commercially available product Fire retardant " the trade name of Daihachi Chemical Industry Co., Ltd.'s manufacture：PX-200”.
Above-mentioned cresyl diphenyl phosphate has the structure represented by following chemical formula (2), and molecular weight is 340.
Above-mentioned phosphoric acid cresol two (2,6- xylyl) ester has the structure represented by following chemical formula (3), and molecular weight is 396。
Fire retardant " the trade name of above-mentioned Daihachi Chemical Industry Co., Ltd.'s manufacture：PX-200 " has following chemical formula (1) Represented structure, molecular weight is 816.
[(CH3)2C6H3O]2P(O)OC6H4OP(O)[OC6H3(CH3)2]2 (1)
In the present embodiment, the boiling temperature (DEG C) of phosphate ester etc. can be measured by known method.It is simple and Speech, boiling temperature is on the basis of known phosphate ester etc., thus it is speculated that molecular weight is higher than more than the boiling temperature of its phosphate ester etc. should Known boiling temperature.For example, when the boiling temperature of triphenyl phosphate (molecular weight 326) is 399 DEG C, thus it is speculated that molecular weight is more than it The compound for boiling temperature more than 399 DEG C such as phosphate ester.Specifically, the above-mentioned phosphoric acid cresol hexichol for exemplifying chemical formula The molecular weight of ester, (2, the 6- xylyl) ester of phosphoric acid cresol two and PX-200 is all higher than triphenyl phosphate, thus it is speculated that boiling temperature is equal More than 399 DEG C.
Also, in the present embodiment, the heat decomposition temperature (DEG C) of phosphate ester etc. can determine dress simultaneously using differential thermal thermogravimetric Put, be measured with 10 DEG C/min of programming rate in air atmosphere, and using tangential method according to its temperature/weight change Curve obtains the temperature that weight starts to change.Simultaneously device is determined as differential thermal thermogravimetric, for example, Seiko electronics industry strain can be used The trade name of formula commercial firm (Seiko Instruments Inc.) manufacture：TG/DTA220, but it is not limited to this.
The phosphate ester of present embodiment is, for example, phosphotriester.
Refer to that 3 hydrogen that phosphoric acid has are substituted by the structure of organic group in this phosphotriester, even if in phosphoric acid Big molecular structure is also illustrated that in ester.It is therefore contemplated that the steric hindrance between easily becoming the hydroxyl that the resin containing phenolic hydroxyl group possesses, The crosslinking between the hydroxyl can well be prevented.
Especially as phosphotriester, triphenyl phosphate or triphenyl phosphate derivant are preferably selected.
This is because, the phenyl contained by phosphoric acid is introduced into using the resin containing phenolic hydroxyl group and is generated as initial substance In a part for the carbon skeleton of material with carbon element, the growth of the crystal structure that can expect to contribute to the material with carbon element.
Triphenyl phosphate derivant refers to that any or all in 3 phenyl of triphenyl phosphate has the change of substituent group Compound.
For example, as the triphenyl phosphate derivant of present embodiment, following chemical formula (1) can be suitably used represented Compound.
[(CH3)2C6H3O]2P(O)OC6H4OP(O)[OC6H3(CH3)2]2 (1)
Phosphoric acid derivatives in present embodiment are substituted by any substituent group and obtain comprising the arbitrary atom for constituting phosphoric acid The compound for arriving or the polyphosphoric acid of condensation reaction thing as phosphoric acid etc..The boiling temperature of polyphosphoric acid is 550 DEG C, is this embodiment party Preferred phosphoric acid derivatives in formula.
The use level of the phosphate ester in the resin combination of present embodiment etc. is not particularly limited, but for example, it is preferable to Relative to the mass parts of resin 100 containing phenolic hydroxyl group, phosphate ester or phosphorus are contained with the scope below more than 3 mass parts 15 mass parts Acid derivative.
In the resin combination of present embodiment, by the way that the use level of phosphate ester etc. is set to more than 3 mass parts, can show The effect that ground plays the crosslinking of the hydroxyl for suppressing the resin containing phenolic hydroxyl group is write, is significantly increased and is generated using the resin combination Material with carbon element battery behavior.Consider from above-mentioned viewpoint, the use level of phosphate ester etc. is more preferably more than 5 mass parts, further It is more than preferably 8 mass parts.
Also, by the way that phosphate ester etc. is set to below 15 mass parts, it can be ensured that in resin combination containing phenolic hydroxyl group The use level of resin is the sufficient degree for generation material with carbon element.
The phosphate ester or phosphoric acid derivatives that the resin combination of present embodiment is used preferably selects fusing point less than containing phenol The material for self condensing temperature of the resin of property hydroxyl.
Thus, in the operation burnt till to resin combination and generated material with carbon element, can be in the resin containing phenolic hydroxyl group Hydroxyls dehydrate condensation and start to start the melting of phosphate ester etc. before crosslinking, phosphate ester in resin combination etc. can be improved Dispersibility.It is well dispersed within resin combination by phosphate ester etc., can be made relative to the resin content containing phenolic hydroxyl group Significantly few phosphate ester etc. effectively plays the effect of the crosslinking for suppressing the hydroxyl in the resin containing phenolic hydroxyl group.
In other words, can avoid by containing phenolic hydroxyl group resin hydroxyl dehydrating condensation cause crosslinking temperature Under, phosphate ester before melting etc. is partly present in the situation in resin combination.
For example, when the hydroxyl of novolak phenolics starts dehydrating condensation at about 300 DEG C, the fusing point of phosphate ester etc. Preferably smaller than 300 DEG C.For example, consider that preferably using triphenyl phosphate, fusing point that fusing point is more than 48.5 DEG C is from above-mentioned viewpoint The aromatic condensation ester of more than 92 DEG C of above-mentioned chemical formula (1), fusing point are about 200 DEG C polyphosphoric acid etc..
Especially in the resin combination of present embodiment, the fusing point and hydroxyl containing phenol of preferably phosphoric acid ester or phosphoric acid derivatives The fusing point of the resin of base exceedes room temperature and for less than 250 DEG C.
Room temperature is exceeded by the fusing point of phosphate ester etc. and the resin containing phenolic hydroxyl group, using dry-mixed preparation resin combination Thing, therefore operability is easy.
Also, less than 250 DEG C are by the fusing point of phosphate ester etc. and the resin containing phenolic hydroxyl group, following effect can be played Really.That is, can be substantially low compared with dehydrating condensation is started with the hydroxyl of the resin containing phenolic hydroxyl group such as novolak phenolics At a temperature of, phosphate ester etc. is melted with the resin containing phenolic hydroxyl group and mix.Thus, can favorably inhibit by containing phenolic hydroxyl group The crosslinking that the dehydrating condensation of the hydroxyl of resin causes.
In addition, in the present embodiment, the fusing point of the fusing point of phosphate ester etc. and the resin containing phenolic hydroxyl group is referred to by differential The temperature of the summit of the endothermic peak that scanning amount thermal analysis system (hereinafter also referred to DSC) is analyzed.
The resin combination of present embodiment, selects used phosphate ester etc. with the resin containing phenolic hydroxyl group so that phosphoric acid Melting end temp of the melting started temperature of ester or phosphoric acid derivatives less than the resin containing phenolic hydroxyl group.
Thus, can start the melting of phosphate ester etc. before the melting of the resin containing phenolic hydroxyl group is fully completed, can improve The compatibility of the resin containing phenolic hydroxyl group and phosphate ester etc..Consider from the viewpoint, more preferably select to melt started temperature and be less than to contain Phosphate ester of the fusing point of the resin of phenolic hydroxyl group etc., and prepare resin combination using them.
In addition, in the present embodiment, melting started temperature refers to the temperature the endothermic peak determined by DSC.Also, In the present embodiment, melt end temp and refer to the temperature that the endothermic peak determined by DSC terminates.
Used as specific illustration, the melting temperature scope of novolak phenolics is 70 DEG C to 100 DEG C.Relative to This, as phosphate ester in present embodiment etc., preferably selects the phosphate ester of fusing point started temperature less than 100 DEG C etc..As this Phosphate ester of sample etc., for example, can enumerate the triphenyl phosphate (commodity manufactured as Daihachi Chemical Industry Co., Ltd. of commercially available product Name：TPP, more than 48.5 DEG C of fusing point) or Daihachi Chemical Industry Co., Ltd. manufacture aromatic condensation phosphate ester (trade name：PX- 200, more than 92 DEG C of fusing point), but it is not limited to this.
Any additive can also be contained as needed in the resin combination of present embodiment.
For example, the resin combination of present embodiment can also contain firming agent.Its reason is that firming agent can promote to contain The heat cure of the resin of phenolic hydroxyl group.
Firming agent is not particularly limited, and determines according to appropriate with the combination of the resin containing phenolic hydroxyl group for being used. For example, in the case where the resin containing phenolic hydroxyl group contained by resin combination is novolak phenolics, can be suitably Using hexamethylenetetramine, resol type phenol resin or polyacetals etc..Also, contained by resin combination containing phenolic hydroxyl group In the case that resin is resol type phenol resin, can be using hexamethylenetetramine etc..
The use level of the firming agent in resin combination is not particularly limited, such as relative to the resin containing phenolic hydroxyl group 100 mass parts are more than 0.1 mass parts below 50 mass parts.
Resin combination especially in the present embodiment uses novolak phenolics as containing phenolic hydroxyl group In the case of resin, can also contain firming agent.
Even if not using firming agent, contained novolak phenolics also can be to the resin group in resin combination Solidify in the operation that compound is burnt till and is carbonized, but it is also possible to generated significantly not hindering to burn till resin combination The scope of growth of crystal structure of material with carbon element contain firming agent.
As the additive beyond firming agent, for example, organic acid, mineral acid, nitrogen-containing compound, oxygen-containing chemical combination can be enumerated Thing, aromatic compound, nonferrous metal element etc..These additives can make according to the species of the resin for being used or character etc. With a kind or it is applied in combination two or more.
Below to the resin containing phenolic hydroxyl group, phosphate ester contained by the resin combination of present embodiment etc. and according to need The additive to be contained is illustrated.The preparation method of the resin combination of the present embodiment containing these materials has no spy Do not limit, can be implemented by appropriate method.For example, by resin, phosphate ester by phenolic hydroxyl group is contained etc. and can be properly added Additive (1) melt the method for mixing, (2) are dissolved in solvent and the method for mixing, (3) are pulverized and mixed method etc. to make It is standby.
Especially in the case where the resin containing phenolic hydroxyl group and phosphate ester of room temperature etc. is exceeded using fusing point, can use above-mentioned (3) method (i.e. dry-mixed).Operability by the resin combination of dry-mixed preparation is easy and preferred.Especially in phosphate ester etc. and The fusing point of the resin containing phenolic hydroxyl group exceed room temperature and for less than 250 DEG C of mode in, can not separately arrange melts them The operation of mixing, and both is melted well in the midway of the operation to being burnt till by the resin combination of dry-mixed preparation Mixing.
As being used to prepare the device of resin combination, it is not particularly limited, for example, is carrying out melting the situation of mixing Under, can be using mixing roller, the uniaxially or biaxially kneading device such as kneader.In the case where melting mixing is carried out, can be using prosperous house The mixing arrangements such as your (Henschel) mixer, allotter (dispenser).In the case of the broken mixing of conducting powder, for example, can Using devices such as hammer mill, aeropulverizers.
The resin combination being achieved in that can be the resin combination for being only physically obtained by mixing Multiple components Thing, or by the mechanical energy that gives in mixing (stirring, mixing etc.) and it is converted when resin combination is prepared Heat energy make one part carry out resin combination obtained from chemical reaction.Specifically, it is also possible to carry out by machinery The mechanico-chemical reaction that can cause or the chemical reaction caused by heat energy.
<Material with carbon element>
Then, the material with carbon element of the present invention is illustrated.Material with carbon element of the invention described below is using the present invention Resin combination manufacture material with carbon element, the surface area of the per unit volume that its particle diameter distribution for containing with good grounds number benchmark is obtained For 10000cm-1Above 16000cm-1The carbon granule of following scope.In addition, being recited as " cm in this manual-1" situation Under, when special instruction is had no, refer to unit " cm2/cm3”.In addition, in the following description, sometimes will be containing preferred carbon The material with carbon element of grain is referred to as material with carbon element.
In addition, material with carbon element described below is not the resin combination to the present invention being limited in any way.The present invention's Resin combination can be suitably used for the manufacture of the material with carbon element beyond the material with carbon element of the present invention.
The lower limit of the surface area of above-mentioned per unit volume can further be set to 12000cm-1More than.Also, above-mentioned per unit The upper limit of the surface area of volume can further be set to 15500cm-1Below or 14000cm-1Below.
The material with carbon element of the present invention is manufactured due to the resin combination using the present invention, therefore charging capacity and efficiency for charge-discharge It is compared with the past to be improved.Also, the material with carbon element of the present invention is above range due to the surface area containing per unit volume Carbon granule, therefore the effect with the resistance increase during discharge and recharge for suppressing secondary cell at low ambient temperatures is (hereinafter also referred to Resistance inhibition).The reason for resistance inhibition is played in the material with carbon element of aforesaid way is still not clear.However, which Material with carbon element it is moderately small with particle diameter, and the surface area of per unit volume becomes fully big mode and constitutes.Thus it is speculated that should The occlusion release efficiency of the lithium ion of the material with carbon element of mode is high, even if at low ambient temperatures the action of lithium ion becomes slow feelings Under condition, occlusion release also can be successfully carried out.In other words, thus it is speculated that the material with carbon element of which is released by making the occlusion as lithium ion The area for putting the surface of the granule in region is significantly increased compared with conventional material with carbon element, makes up for the shifting of the lithium ion under low temperature environment The reduction of dynamic property, and suppress the increase of resistance.
Specifically, the surface area that above-mentioned material with carbon element passes through per unit volume is 10000cm-1More than, as lithium ion The gross area of the particle surface of occlusion release areas is fully big.Thus, material with carbon element of the invention is compared with conventional material with carbon element, lithium The occlusion releasability of ion is excellent, even if can also play resistance inhibition at low ambient temperatures.
Also, it is 16000cm by the way that above-mentioned material with carbon element to be set to the surface area of per unit volume-1Following scope, can arrange Except the granule of extremely small material with carbon element.When in material with carbon element containing extremely small material with carbon element granule when, during high temperature from Trend of the discharge capacity in increasing, also, when the material paste containing material with carbon element is coated on collector, because of the slurry The notable rising of the viscosity of material, trend of the coating in reducing.Consider from the viewpoint, material with carbon element is preferably per unit volume The upper limit of surface area is 16000cm-1。
The present invention material with carbon element in, the resistance under low temperature environment can according to regulation cold environmental conditions under (for example- 20 DEG C of environment) size of value of D.C. resistance (DC-IR) that determines judged.In the relatively large situation of DC resistance Under, it is judged as that resistance is of a relatively high.
In the material with carbon element of the present invention, the particle diameter distribution of number benchmark refer to by laser diffraction/scattering method obtain The accurate particle diameter distribution of base.The particle diameter distribution can be measured using laser diffraction/scattering formula particle size distribution device.Example Such as, LA-920 for manufacturing using Horiba Ltd (HORIBA, Ltd.) etc. is measured.Refer in this particle diameter The diameter of grain.
In the present invention, the surface area of the per unit volume obtained according to the particle diameter distribution of number benchmark, can use basis The number that the particle diameter distribution of the number benchmark determined by arbitrary laser diffraction/scattering formula particle size distribution device is obtained According to using following mathematical expressions (1) calculating.
Surface area (the cm of per unit volume-1)=total surface area (cm2)/cumulative volume (cm3)(1)
Here " total surface area " is that the surface area when granule of each particle diameter in particle diameter distribution is scaled into just spherical is multiplied by The summation being worth obtained from the frequency (%) of the granule of each particle diameter.
Also, " cumulative volume " is that the volume when granule of each particle diameter in particle diameter distribution is scaled into just spherical is multiplied by each grain The summation being worth obtained from the frequency (%) of the granule in footpath.
Also, " frequency " is the ratio of the granule relative to the total particle number for determining of each particle diameter.
Obtain the carbon materials of the carbon granule of the surface area containing the per unit volume with the preferred scope determined in the present invention The method of material is not particularly limited, and used as an example, can enumerate suitably carries out pulverization process during manufacture material with carbon element. The detailed content of pulverization process will be described hereinafter.
The mean square radius of gyration (hereinafter also referred to as mean square half that the material with carbon element of the present invention is preferably obtained according to above-mentioned particle diameter distribution Footpath) it is 1 μm24 μm of the above2Following scope.
That is, it is 1 μm by the above-mentioned mean square radius of gyration2More than, can be by the carbon contained by the significantly small granule from material with carbon element of particle diameter Exclude in granule, prevent the deterioration of self discharge under hot environment, and maintain the coating to collector well.Also, it is logical The above-mentioned mean square radius of gyration is crossed for 4 μm2Hereinafter, the carbon for easily selecting the surface area of per unit volume to be contained in above-mentioned preferred scope Grain.
Solve expected from the present invention from the viewpoint of problem from well, the upper limit of the above-mentioned mean square radius of gyration is more preferably set to 3 μ m2Hereinafter, 2 μm are further preferably set to2Below.
The mean square radius of gyration obtained according to above-mentioned particle diameter distribution in the optimal way of the present invention can be according to the grain of number benchmark Footpath distribution is obtained.Specifically, can use according to by arbitrary laser diffraction/scattering formula particle size distribution device measure The data that the particle diameter distribution of number benchmark is obtained, are calculated using following mathematical expressions (2).
The mean square radius of gyration (μm2The radius of)=each granule square summation (μm2) (2)
Here " radius of each granule square summation (μm2) " be with particle diameter distribution in each particle diameter 1/2nd values As radius, value obtained from its square is multiplied by into the summation of value obtained from the frequency of the granule of each particle diameter (%).
In one of optimal way of material with carbon element of the present invention, the true specific gravity of the carbon granule contained by material with carbon element is 1.5g/cm3With Upper 1.7g/cm3Following scope.
It is 1.5g/cm by selecting true specific gravity3Carbon granule above, can make the value stabilization of charge/discharge capacity.Also, pass through Selection true specific gravity is 1.7g/cm3Following carbon granule, is favorably improved the life-span of the secondary cell using material with carbon element of the invention Characteristic.
Above-mentioned true specific gravity can be obtained by using the true specific gravity assay method of butanol.
Be adjusted so that the present invention material with carbon element contained by carbon granule become above-mentioned preferred scope true specific gravity method It is not particularly limited, for example, true ratio can be adjusted by the heating condition of the raw material of the selected or material with carbon element of the raw material of material with carbon element Weight.
The mode that the carbon granule in the material with carbon element of the present invention contains hard carbon is illustrated below.For example, in the present invention Carbon granule is preferably comprised more than 80 mass %, more than further preferably 90 mass %, more than particularly preferably containing 95 mass % The hard carbon of the description below.
That is, as one of optimal way of material with carbon element of the invention, the carbon granule contained by the material with carbon element can be containing by making The centre plane interval d in (002) face obtained as radiogenic X-ray diffraction method with CuK alpha rays002For more than 0.340nm's Hard carbon.
Hard carbon (difficult graphitization carbon) is that the carbon that the macromolecule of prosperity is burnt till and obtained is difficult to crystal structure of graphite Material, is the material of amorphous (amorphous).In other words, hard carbon is the not material with carbon element or only partially with graphene-structured Carbon with graphene-structured, with above-mentioned specific centre plane d is spaced002.D is spaced in the centre plane of hard carbon002For 0.340nm Above, in the case of especially more than 0.360nm, it is difficult to which contraction, the expansion of the interlayer associated with the occlusion of lithium ion occur, therefore The reduction of charge-discharge cycle can be suppressed.Centre plane is spaced d002The upper limit and not specially provided, can for example be set to 0.390nm with Under.D is spaced in above-mentioned centre plane002In the case of for below 0.390nm, especially below 0.380nm, lithium can be successfully carried out The occlusion release of ion, can suppress the reduction of efficiency for charge-discharge.
Further, size Lc of the crystallite of the preferred c-axis direction of above-mentioned hard carbon ((002) face orthogonal direction) is more than 0.8nm 5nm Below.
By the way that Lc to be set to more than 0.8nm, especially be set to more than 0.9nm, can occlusion release lithium ion with being formed Carbon interlayer space, obtains the effect of sufficient charge/discharge capacity, by the way that Lc to be set to below 5nm, especially be set to below 1.5nm, Disintegrate with the carbon-coating stack structure that the occlusion release by lithium ion can be suppressed to cause or the reduction decomposition of electrolyte, and suppress to fill The effect of the reduction of discharging efficiency and charge-discharge cycle.
Lc is calculated as follows.
The half breadth and the angle of diffraction at the 002 face peak in the spectrum obtained by X-ray diffraction measure, using following Scherrer formula (Scherrer formula) and determine.
Lc=0.94 λ/(β cos θ) (Scherrer formula)
Lc：The size of crystallite
λ：From the wavelength of the characteristic X-ray K α 1 of negative electrode output
β：The half breadth (radian) at peak
θ：The reflection angle of spectrum
The X-ray diffraction spectra of hard carbon can be manufactured by Shimadzu Scisakusho Ltd (Shimadzu Corporation) X-ray diffraction device " XRD-7000 " be measured.The assay method at the above-mentioned centre plane interval of hard carbon is for example following.
Can be according to the spectrum obtained by X-ray diffraction measure of hard carbon, by following Bragg formula (bragg's formula) Centre plane interval d is calculated as follows.
λ=2dhklsin θ (Bragg formula) (dhkl=d002)
λ：From the wavelength of the characteristic X-ray K α 1 of negative electrode output
θ：The reflection angle of spectrum
As the characteristic that the carbon granule of hard carbon discharges with the occlusion that can carry out lithium ion in its whole surface.Therefore, contain There is the material with carbon element of the carbon granule of the hard carbon of the surface area of the per unit volume for showing above range, show because of the increase of surface area The excellent effect of the occlusion releasability of lithium ion has been given play to writing.That is, the carbon of the invention containing the carbon granule as hard carbon Material can be enjoyed fully by the effect for constituting generation of the present invention, given play to excellent effect.
Also, usually as hard carbon carbon granule compared with the carbon granule as graphite, there is intragranular lithium ion The low problem of diffusibility (mobility).In contrast, the carbon granule as hard carbon contained by the material with carbon element of the present invention is by per single The surface area of position volume is above-mentioned preferred scope, and carbon granule can make up for above-mentioned diffusibility not by fully micronized It is good.Consider from the viewpoint, in the present invention, meet above-mentioned excellent by the surface area of per unit volume as the carbon granule of hard carbon Scope is selected, the raising of the occlusion releasability of lithium ion is notable.
From fully enjoying as described above by from the viewpoint of the effect that obtains containing hard carbon in carbon granule, this Carbon granule in bright can be containing hard carbons more than 90 mass %.
But, the material with carbon element of the present invention is not precluded from the mode containing graphite.Refer to that a kind of homoatomic of carbon is different in this graphite Body, is hexagonal crystal system, the material of hexagonal platelike crystal to form the layer winding that the layer being connected by hydrogenation of six carbocyclic is formed.On State graphite and there is so-called graphene-structured.Above-mentioned graphite includes native graphite and Delanium.
Graphite has from the electric discharge initial stage to the few preferred property of electric discharge latter stage change in voltage, can maintain stable high voltage Till electric discharge latter stage.Part or all of carbon granule contained by the material with carbon element of the present invention can be made up of graphite.
Balance from the viewpoint of good material with carbon element from being utilized respectively the advantage of hard carbon and graphite, providing, the carbon of the present invention Carbon granule in material can be containing hard carbon and graphite.
Containing both hard carbon and graphite as carbon granule mode of the invention, under microscopic visualization, comprising：Hard carbon Granule and graphite granule situation about separately being observed；With both merge or bond and it is whole with one in appearance The situation that body is observed.
Hard carbon in the material with carbon element of the present invention is not particularly limited with the containing ratio of graphite.However, a large amount of from passing through Surface area containing per unit volume is played from the viewpoint of above-mentioned resistance inhibition for the hard carbon in prescribed limit, excellent Elect following ratio ranges as.Both that is, in the material with carbon element of the invention containing hard carbon and the mode of graphite, in material with carbon element Mass ratio is preferably hard carbon: graphite=51 mass %: 49 mass % are to 95 mass %: the scope of 5 mass %.
The material with carbon element of the present invention discussed above substantially only can be made up of carbon granule, it is also possible to containing it is arbitrary its His material.For example, material with carbon element of the invention contains above-mentioned carbon granules more than 90 mass %, preferably comprises more than 95 mass % Above-mentioned carbon granule.
And, although reason is still not clear, but is formed using the secondary battery negative pole resin combination of the present invention Secondary battery negative pole material with carbon element, not only can play excellent property in above-mentioned low-temperature characteristics evaluation, and can be in height Excellent property is played under warm environment.That is, according to the two of the negative pole for possessing the secondary battery negative pole material with carbon element containing the present invention Primary cell, the excellent discharge capacity that more than 85% is can be shown that in High temperature storage characteristic evaluation is maintained.Also, according to possessing The secondary cell of the negative pole of the secondary battery negative pole material with carbon element containing the present invention, can be shown that in life characteristics at high temperature evaluation More than 85% excellent discharge capacity is maintained.
That is, secondary battery negative pole material with carbon element of the invention is the secondary battery negative pole carbon materials for secondary battery negative pole Material, the High temperature storage characteristic for preferably showing in following High temperature storage characteristic evaluations is more than 85%.
During High temperature storage characteristic in the present invention is evaluated, using lithium rechargeable battery, the lithium rechargeable battery possesses： Secondary battery negative pole containing secondary battery negative pole material with carbon element；Positive pole, the electrolyte solution containing dissolving；And barrier film.
Here, the secondary battery negative pole containing secondary battery negative pole material with carbon element is referred in negative electrode active material containing secondary The secondary battery negative pole of battery cathode material with carbon element.Also, containing lithium and cobalt oxides (LiCoO2) positive pole refer to positive-active Anode of secondary battery containing lithium and cobalt oxides in material.The positive pole is using by using the single-layer sheet of aluminium foil (Pionics strain formulas Commercial firm manufactures, trade name：Pioxcel C-100) be formed as diameter 12mm it is discoid obtained from material as collector Made by.
It is above-mentioned just extremely to contain lithium and cobalt oxides (LiCoO2) positive pole be appropriate.
Specifically, above-mentioned electrolyte is in ethylene carbonate and the mixed liquor of diethyl carbonate with the concentration of 1 mol/L The electrolyte for dissolving lithium hexafluoro phosphate in (volume ratio 3: 7) and preparing is appropriate.
Above-mentioned barrier film is appropriate for polypropylene perforated membrane.
The detailed content of the High temperature storage characteristic in the present invention is as described below.That is, using above-mentioned lithium rechargeable battery, enter The charge and discharge cycles for being about to specify implement 5 burin-in process for circulating, and to the 5th electric discharge for circulating of the charge and discharge cycles When discharge capacity be measured and be set to discharge capacity I.Using the lithium rechargeable battery after above-mentioned burin-in process, by electric current Density is set to 25mA/g and carries out constant-current charge, from the moment that current potential reaches 4.2V, further keeps 4.2V and carries out constant pressure and fill Electricity, charges to till electric current density reaches 2.5mA/g, and preparation is adjusted to charged state (State of Charge；SOC) 100% Lithium rechargeable battery, by the lithium rechargeable battery of above-mentioned charged state 100% the temperature for being adjusted to 60 DEG C drying Take care of 1 week in machine.And after keeping, using the lithium rechargeable battery, charged and discharged with the current value of 0.2C, with This implements the discharge and recharges of total 3 circulations as 1 circulation, discharge capacity when determining the electric discharge of the 3rd circulation and be set to put Capacitance II, according to following mathematical expressions (4) High temperature storage characteristic is calculated.
High temperature storage characteristic (%)=[discharge capacity II (mAh/g)/discharge capacity I (mAh/g)] × 100 (4)
In addition, the charge and discharge cycles for specifying in the present invention are referred to using above-mentioned lithium rechargeable battery, by temperature of the measurement 25 DEG C are set to, electric current density when charging is set to into 25mA/g carries out constant-current charge, from the moment that current potential reaches 4.2V, are kept 4.2V and carry out constant-voltage charge, charge to till electric current density reaches 2.5mA/g, then, electric current density during electric discharge is set to 25mA/g, carries out constant-current discharge, is discharged to current potential and reaches 2.5V, in this, as 1 circulation.Further enter under identical condition Row charging and discharging, implements the discharge and recharge of total 5 circulations.In above-mentioned burin-in process, the putting during electric discharge circulated to the 5th Capacitance (discharge capacity I) is measured.
High temperature storage characteristic evaluation in accordance with the above, by the way that the condition beyond secondary battery negative pole material with carbon element is united One, can be to being evaluated based on the High temperature storage characteristic of the secondary battery negative pole material with carbon element for evaluating.
Also, the secondary battery negative pole material with carbon element of the present invention is the secondary battery negative pole carbon for secondary battery negative pole Material, the life characteristics at high temperature for preferably showing in following life characteristics at high temperature evaluations is more than 85%.
Life characteristics at high temperature evaluation in the present invention uses secondary with the lithium that above-mentioned High temperature storage characteristic evaluation is used The same secondary cell of battery is implementing.
The detailed content of the life characteristics at high temperature in the present invention is as described below.That is, using above-mentioned lithium rechargeable battery, enter The charge and discharge cycles for being about to specify implement 5 burin-in process for circulating.Also, using the lithium ion secondary after above-mentioned burin-in process Battery, implements following charge and discharge cycles, in this, as 1 circulation：Under 55 DEG C of temperature environment with the constant-current charge of 1C extremely 4.2V, afterwards, is decayed to after 0.02C with the constant-voltage charge of 4.2V to current value, is kept for 30 minutes under 55 DEG C of temperature environment, Then, with the constant-current discharge of 1C to 2.5V, and determine discharge capacity and be set to discharge capacity III, afterwards, in 55 DEG C of temperature Kept for 30 minutes under environment.Then, further above-mentioned charge and discharge cycles are implemented into 99 to circulate, and implements total 100 circulations Charge and discharge cycles, and determine the 100th circulation electric discharge when discharge capacity and be set to discharge capacity IV, according to following numbers Formula (5) calculates life characteristics at high temperature.
Life characteristics at high temperature (%)=[discharge capacity IV (mAh/g)/discharge capacity III (mAh/g)] × 100 (5)
In addition, during the charge and discharge cycles of the regulation in life characteristics at high temperature evaluation are evaluated with above-mentioned High temperature storage characteristic The charge and discharge cycles of regulation are identical, therefore here does not elaborate.
Life characteristics at high temperature evaluation in accordance with the above, by the way that the condition beyond secondary battery negative pole material with carbon element is united One, can be to being evaluated based on the life characteristics at high temperature of the secondary battery negative pole material with carbon element for evaluating.
As previously discussed, the secondary cell for being formed using the carbon material for negative electrode of the present invention, even if at 60 DEG C or so In the case of taking care of for a long time under hot environment, it is also possible to which high ratio maintains the discharge capacity before keeping.
Also, the secondary cell formed using the carbon material for negative electrode of the present invention, even if in 55 DEG C or so of high temperature ring Under border in the case of Reusability, it is also possible to which high ratio maintains the discharge capacity before Reusability in high temperature environments.
Therefore, secondary cell material with carbon element of the invention can provide it is tolerable take care of in high temperature environments or use it is secondary Battery.
<The manufacture method of secondary battery negative pole material with carbon element>
Then, to being carried out specifically with the mode of the manufacture method of material with carbon element for implementing secondary battery negative pole of the invention It is bright.The material with carbon element manufacture method of the present invention is using above-mentioned resin combination manufacture secondary battery negative pole carbon materials of the invention The method of material.
The material with carbon element manufacture method of present embodiment has the first firing process and the second firing process.
Firing condition of maximum temperature when first firing process is to burn till less than 1000 DEG C is used secondary battery negative pole Resin combination is burnt till and is generated the operation of material with carbon element precursor.
Maximum temperature when second firing process is to burn till is that the firing condition of more than 1000 DEG C of temperature burns to first Burnt till into the material with carbon element precursor generated in operation, thus generated the operation of material with carbon element.
First firing process and the second firing process can continuously be implemented, and also can be performed separately.
As the example of the mode for being performed separately the first operation and the second operation, for example can be in the first firing process and the The pulverizing process that the material with carbon element precursor that will be obtained by the first firing process is crushed is set between two firing process.From making the second burning Into the material with carbon element precursor in operation thermal process become uniform from the viewpoint of, be preferable to carry out above-mentioned pulverizing process.Above-mentioned crushing The particle diameter of the ground product of the material with carbon element precursor obtained in operation is not particularly limited, and is less than more than 1 μm 20 μm, more preferably Less than more than 5 μm 15 μm.Particle diameter by above-mentioned ground product is more than the lower limit of the above-mentioned numerical range operability of ground product Well, and the phosphorus contained by phosphate ester etc. can be made significantly to remain in the material with carbon element being ultimately formed.Also, by above-mentioned crushing The particle diameter of thing is the thermal process that the material with carbon element in the second firing process can be well realized below the higher limit of above-mentioned numerical range Homogenization.
The particle diameter of above-mentioned ground product refers to particle diameter (D50, average grain during 50% accumulation in the cumulative distribution of volume reference Footpath).
Also, the pulverization conditions in by adjusting above-mentioned pulverizing process, can manufacture containing the per unit body for preferred scope Long-pending surface area or the material with carbon element of the carbon granule of the mean square radius of gyration.
Breaking method in above-mentioned pulverizing process is not particularly limited, for example, can use arbitrary reducing mechanism.As upper Reducing mechanism is stated, device can be listed below, but be not limited to this：Ball mill apparatus, vibrator device, rod mill dress Put, the air-flow such as impingement reducing mechanism or airswept mill device, aeropulverizer device, dry type air flow crushing device such as bead mill apparatus Reducing mechanism.In pulverization process, these devices can use one or more, or can be carried out repeatedly by a kind of device Crush and use.Also, in pulverization process, in addition to these devices, it is possible to use sieve etc. is suitably classified, also, Also the reducing mechanism with grading function can be used.
The material with carbon element manufacture method of present embodiment is given birth in the first firing process comprising melting stage and material with carbon element precursor Into the stage.
The above-mentioned melting stage makes the resin containing phenolic hydroxyl group and the phosphate ester contained by secondary battery negative pole resin combination Or phosphoric acid derivatives melt.
Above-mentioned material with carbon element precursor generation phase forms the crystallite containing defat and/or the preferred carbon of class graphene-structured.
The carbon manufacture method of present embodiment is preferably spread out in the phosphorus compound or phosphoric acid for making to be melted by the above-mentioned melting stage Before biology boiling or decomposition, the resin containing phenolic hydroxyl group to being melted by the melting stage is heated, and thus generates material with carbon element Precursor.
In the first firing process, in order to realize above-mentioned melting stage and above-mentioned material with carbon element precursor generation phase, for example, make Exceed room temperature with the fusing point of the resin containing phenolic hydroxyl group and phosphate ester contained by resin combination etc. and the tree for less than 250 DEG C Oil/fat composition.Thus, the resin containing phenolic hydroxyl group can self condense in for the firing process of carbide resin compositionss The resin containing phenolic hydroxyl group and phosphate ester etc. is set to melt (melt the stage) before beginning.
By further under high temperature (such as less than more than 300 DEG C 800 DEG C) to existing through the melting stage containing phenol The resin combination of the resin and phosphate ester of hydroxyl etc. is burnt till, and can contain defat and class by the resin formation containing phenolic hydroxyl group The crystallite of the preferred carbon of graphene-structured, and form material with carbon element precursor.In the material with carbon element manufacture method of present embodiment, by Phosphate ester before it there is boiling or thermally decompose in material with carbon element precursor generation phase etc., therefore the resin containing phenolic hydroxyl group can be suppressed Hydroxyl situation about being crosslinked by dehydrating condensation.Result, it is believed that the crystal structure of the material with carbon element precursor for being generated be lithium from The structure that the excellent established structure of crystallite of the occlusion releasability of the chemical species such as son or the crystallite are being formed.
In the material with carbon element manufacture method of present embodiment, the above-mentioned melting stage and material with carbon element precursor generation phase can be Independently start the mode of material with carbon element precursor generation after the melting stage is fully completed in the first firing process or melt the stage Any one in the Chong Die mode of front half section that second half section generates with material with carbon element precursor.
In the first firing process, melt the stage and material with carbon element precursor generation phase can be by the resin containing phenolic hydroxyl group Reduction or expansion with the volume of phosphate ester etc. is measured and judges.That is, will pass through to burn till in the first firing process to make to contain The thermal meltings such as the resin and phosphate ester of phenolic hydroxyl group and have the tendency of volume reduction stage be referred to as the melting stage.Also, will be The volume of the resin containing phenolic hydroxyl group reduced because of melting in the first firing process shows that the stage of expansion is referred to as material with carbon element Precursor generation phase.
Above-mentioned the first firing process and the gas atmosphere of the second firing process is not particularly limited, for example can be in torpescence Carry out under gas atmosphere.As above-mentioned inactive gas, nitrogen, argon, helium etc. can be enumerated.In these gases, particularly preferably Nitrogen.
The gas atmosphere of the first firing process and the second firing process may be the same or different.
The conditions such as programming rate, firing temperature, firing time in the first firing process and the second firing process can be in order to Making the characteristic of the predetermined negative pole for using generated material with carbon element becomes optkmal characteristics and is suitably adjusted.
Material with carbon element manufacture method by more than, can obtain secondary battery negative pole material with carbon element.By present embodiment The charge/discharge capacity and efficiency for charge-discharge of the material with carbon element manufactured by material with carbon element manufacture method is improved, and battery behavior is excellent.
The negative electrode active material that secondary battery negative pole is used can be used as by the material with carbon element manufactured by present embodiment.
In addition, the manufacture method of the secondary battery negative pole material with carbon element of the present invention discussed above uses the present invention One example of the method for resin combination manufacture material with carbon element, it is not excluded that use the present invention's by other manufacture method manufactures The situation of the material with carbon element of resin combination.
Hereinafter, to containing using the present invention resin combination material with carbon element negative electrode active material, possess containing The secondary battery negative pole of the negative electrode active material layer of the negative electrode active material and possesses the secondary cell of the secondary battery negative pole Illustrate.
<Negative electrode active material>
Hereinafter, to the negative electrode active of the invention containing the above-mentioned material with carbon element generated using the resin combination of the present invention Material is illustrated.
Negative electrode active material be in the secondary cells such as alkali metal-ion battery can occlusion and release alkali metal ion (for example Lithium ion or sodium ion) etc. chemical species material.Illustrated negative electrode active material is referred to containing using this in this specification The material of the material with carbon element that the resin combination of invention is generated.
Negative electrode active material substantially only can be made up of material with carbon element, also can also contain the material different from material with carbon element.As This material, for example, can enumerate silicon, silicon monoxide, graphite material etc. usually as negative material known material.
Wherein, negative electrode active material contains graphite material preferably in addition to above-mentioned material with carbon element.Thus, alkali can be improved The charge/discharge capacity of the secondary cells such as metal ion battery.The material with carbon element generated using the resin combination of the present invention is not only filled Discharge capacity is improved, and efficiency for charge-discharge is also improved, therefore the charging that will can be come by addition graphite material strips Capacity raising reflection in the raising of efficiency for charge-discharge and it is preferred that.
Particle diameter (mean diameter) when in the cumulative distribution of the volume reference of the graphite material for being used 50% is accumulated It is preferred that less than more than 2 μm 50 μm, more preferably less than more than 5 μm 30 μm.
<Secondary battery negative pole and secondary cell>
Hereinafter, to the secondary battery negative pole of the invention with above-mentioned negative electrode active material and possessing the secondary battery cathode The secondary cell of the invention of pole is illustrated.
The secondary battery negative pole of the present invention is characterised by having：The secondary battery cathode of the active substance containing the present invention Pole active material layer；With the negative pole collector for being laminated with secondary battery negative pole active material layer.
Also, the secondary cell of the present invention is characterised by, possess secondary battery negative pole, the electrolyte and secondary of the present invention Anode.
The secondary battery cathode (hereinafter also referred to as negative pole) of the present invention is used manufactured by above-mentioned negative electrode active material 's.Thus, it is possible to provide the excellent negative pole of charging capacity and efficiency for charge-discharge.
Also, the secondary cell of the present invention is manufactured using the negative pole described in this specification.Thus, it is possible to provide fill The excellent secondary cell of capacitance and efficiency for charge-discharge.
Also, using the present invention material with carbon element negative pole of the invention and possess the secondary cell of the negative pole low The increase of the resistance under warm environment is suppressed, and can play excellent battery performance.Therefore, negative pole of the invention and possesses this The secondary cell of negative pole can launch in a variety of applications where.
As above-mentioned secondary cell, for example, the alkali metal such as lithium rechargeable battery or sodium ion secondary battery two can be enumerated Primary cell, but it is not limited to this.Also, above-mentioned secondary cell includes nonaqueous electrolytic solution secondary battery and solid secondary battery Deng the various forms using different electrolyte.In the following description, enter by taking lithium rechargeable battery as an example as secondary cell Row explanation.
Hereinafter, using Fig. 1, to possessing containing the of the invention of the material with carbon element generated using the resin combination of the present invention One example of the lithium rechargeable battery of negative pole is illustrated.Fig. 1 is to represent the resin combination institute containing using the present invention The schematic diagram of one example of the lithium rechargeable battery 100 of a mode as the present invention of the material with carbon element of generation.Negative pole 10 is the negative pole of the present invention.
Lithium rechargeable battery 100 is as shown in figure 1, have negative pole 10, positive pole 20, barrier film 30 and electrolyte 40.
Negative pole 10 is as shown in figure 1, have negative electrode active material layer 12 and negative electrode collector 14.
Negative electrode active material layer 12 is containing the material with carbon element using above-mentioned resin combination of the invention.
As negative electrode collector 14, it is not particularly limited, can generally uses known negative pole collector, for example, can makes With Copper Foil or nickel foil etc..
Negative pole 10 for example can be carried out as follows manufacture.
Relative to the above-mentioned mass parts of negative electrode active material 100, organic polymer binding agent (example generally known to addition Such as, the fluorine system macromolecule such as polyvinylidene fluoride, politef；SBR styrene butadiene rubberses, butyl rubber, butadiene rubber Etc. rubber-like macromolecule etc.) below more than 1 mass parts 30 mass parts and solvent (N- methyl -2- pyrroles is used in appropriate viscosity adjustment Alkanone, dimethylformamide, alcohol, water etc.) or water kneaded, and prepare cathode size.
Also, also can further add conductive material to above-mentioned negative electrode active material as needed.As conductive material, Any one of acetylene black, Ketjen black, gas-phase growth of carbon fibre etc. can for example be used or combined.The use level of conductive material has no spy Do not limit, such as in mass % of negative electrode active material 100, more than preferably 2 mass % below 10 mass %, further preferred 3 More than quality % below 7 mass %.Also can use outside these scopes, if but conductive agent use level it is excessive, it is likely that deposit Be needed for negative electrode active material quality in electrode is reduced more than, and the volume capacity for being possible to negative pole is reduced.
Lamellar, partical etc. are configured to as the slurry by obtained by such as compression molding, roller shaping, negative electrode active material can be obtained Matter layer 12.Also, the negative electrode active material layer 12 so obtained by stacking and negative electrode collector 14, can obtain negative pole 10.
Also, by coating on negative electrode collector 14 and being dried the cathode size of acquisition, can also manufacture negative pole 10。
Electrolyte 40 is filled up between positive pole 20 and negative pole 10, is the layer of lithium ion movement by discharge and recharge.
As electrolyte 40, it is not particularly limited, can generally uses known electrolyte, for example, is usable in non-water system The nonaqueous electrolytic solution of the lithium salts for becoming electrolyte is dissolved with solvent.
As the non-water solvent, for example, can use：The cyclic esters such as Allyl carbonate, ethylene carbonate, gamma-butyrolacton Class；The chain esters such as dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate；The chain ethers such as dimethoxy-ethane；Or they Mixture etc..
As electrolyte, it is not particularly limited, can generally uses known electrolyte, for example, LiClO can be used4、LiPF6 Etc. lithium metal salt.Also, also above-mentioned salt and poly(ethylene oxide), polyacrylonitrile etc. can be mixed, as solid electrolyte.
As barrier film 30, be not particularly limited, can generally use known barrier film, for example, can using using polyethylene or Perforated membrane, non-woven fabrics that polypropylene etc. is constituted etc..
Positive pole 20 is as shown in figure 1, have positive electrode active material layer 22 and positive electrode collector 24.
As positive electrode active material layer 22, it is not particularly limited, generally can be formed by known positive active material.Make For positive active material, it is not particularly limited, for example, can uses：Lithium and cobalt oxides (LiCoO2), lithium nickel oxide (LiNiO2)、 Lithium manganese oxide (LiMn2O4), nickle cobalt lithium manganate (LiNixCoyMnzO2, x+y+z=1) etc. composite oxides：Polyaniline, poly- pyrrole The electroconductive polymer etc. such as cough up.
Positive active material is in the same manner as above-mentioned negative electrode active material containing organic polymer binding agent and conductive material. The use level of organic polymer binding agent and conductive material in positive active material is not particularly limited, and can be set to be lived with negative pole Property material is identical, also, can also coordinate the amounts different from negative electrode active material.
As positive electrode collector 24, it is not particularly limited, can generally uses known positive electrode collector, for example, can uses Aluminium foil, stainless steel foil, titanium foil, nickel foil, Copper Foil etc..
Also, the positive pole 20 in present embodiment generally can be manufactured by the manufacture method of known positive pole.
More than, it is illustrated by taking lithium rechargeable battery 100 as an example, but the above-mentioned tree being not precluded from the present invention is used The situation of the secondary cell that the material with carbon element that oil/fat composition is generated is used for beyond lithium rechargeable battery.Using the resin of the present invention The material with carbon element that compositionss are generated can also be used for the basic ion using beyond the lithium ions such as such as sodium ion as the two of chemical species Primary cell.Now, each basic ion secondary cell can use same with the part that above-mentioned lithium rechargeable battery 100 is used Part and constitute, it is possible to use different part and constitute.For example, in the negative electrode collector in sodium ion secondary battery, except Beyond above-mentioned illustrated negative electrode collector, aluminium foil also may be selected.
More than, embodiments of the present invention are illustrated, but these are the illustration of the present invention, be may also be employed above-mentioned Various compositions in addition.For example, in FIG, it has been shown that be formed with negative electrode active in the face of the wherein side of negative electrode collector 14 Material layer 12 and it is formed with the example of positive electrode active material layer 22 in the face of the wherein side of positive electrode collector 24.As change Example, also can form negative electrode active material layer 12 on the two sides of negative electrode collector 14, and on the two sides of positive electrode collector 24 positive pole is formed Active material layer 22, and make them opposed across barrier film 30 and electrolyte 40, and constitute secondary cell.
Also, the present invention is not limited to aforesaid embodiment, the change in the range of the purpose of the present invention is being can reach Shape, improvement etc. are also included in the present invention.
Secondary cell can properly configure negative pole 10, positive pole 20, barrier film 30 and electrolyte 40 in mutually fitting with secondary cell Formed in the housing answered.The type of secondary cell is not specified, for example, can enumerate cylinder type, Coin shape, square or membranous type Deng.
Then, the 2nd aspect of the present invention is illustrated.With regard to first method Aspect identical, substantially omit note Carry, and illustrated centered on the aspect different from first method.
The present inventor is in order to provide the initial substance by the use of phenolic resin as secondary battery negative pole material with carbon element, and charge and discharge Electrical efficiency improved secondary battery negative pole material with carbon element and the secondary cell using the secondary battery negative pole material with carbon element Negative electrode active material, secondary battery negative pole and secondary cell, are studied.
It can be seen from the studies above, containing substantial amounts of phenol and hydroxyl on main chain as novolak phenolics The efficiency for charge-discharge of the little phenolic resin of base equivalent is simultaneously insufficient.The present inventor speculates that its reason is as described below.In addition, phenolic aldehyde is clear The hydroxyl equivalent of paint shaped phenolic resin is 105g/eq.
I.e., thus it is speculated that in the firing process for being burnt till and being generated material with carbon element for the phenolic resin little to hydroxyl equivalent, At least a portion for the hydroxyl that the phenolic resin possesses is in intramolecular or intermolecular carry out dehydrating condensation and is crosslinked.Think due to There are the following problems for the crosslinking material with carbon element：The growth of crystal structure during generation is hindered, it is difficult to is formed and contains class Graphene The crystallite (hereinafter sometimes referred to simply as " problem of the crosslinking of hydroxyl ") of the preferred carbon of structure.As a result, speculating the material with carbon element The occlusion releasability of the chemical species such as lithium ion is insufficient, it is difficult to play excellent efficiency for charge-discharge.Referring in this crystallite can It is considered as the maximum set body of monocrystalline.
Therefore, the present inventor completes the present invention by further investigation based on following technological thought：By using with hydroxyl Equivalent becomes the phenolic resin that mode more than prescribed limit is modified, and the problem of the crosslinking of hydroxyl is improved, and its result can change Kind efficiency for charge-discharge.
Hereinafter, it is (hereinafter also referred to as modified to contain phenol with the modified resin containing phenolic hydroxyl group to secondary battery negative pole successively The resin of hydroxyl), secondary battery negative pole material with carbon element (hereinafter also referred to as material with carbon element), secondary battery negative pole active substance (with Be also referred to as negative electrode active material down), secondary battery negative pole (hereinafter also referred to as negative pole) and secondary cell illustrate.
<The secondary battery negative pole resin containing phenolic hydroxyl group that is modified>
Hereinafter, the mode of the resin combination to being used to implement the present invention is described in detail.
The secondary battery negative pole of present embodiment is characterised by that hydroxyl equivalent is with the modified resin containing phenolic hydroxyl group More than 115g/eq.
Using the material with carbon element that the modified resin containing phenolic hydroxyl group is generated as initial substance, with use such as phenolic varnish type The conventional material with carbon element of resin of the such hydroxyl equivalent of phenolic resin less than 115g/eq is compared, and efficiency for charge-discharge is changed It is kind.That is, the modified resin containing phenolic hydroxyl group in present embodiment is used as the starting material for generating the excellent material with carbon element of battery behavior Matter is useful.
As described above, the hydroxyl equivalent of the modified resin containing phenolic hydroxyl group of present embodiment is more than 115g/eq, it is more excellent Elect more than 130g/eq, more preferably more than 150g/eq as.The hydroxyl equivalent being considered more than above-mentioned setting it is modified In resin containing phenolic hydroxyl group, the problem of the crosslinking of hydroxyl is significantly improved.Also, examine from the viewpoint of the crosslinking for suppressing hydroxyl Consider, the upper limit of hydroxyl equivalent is not particularly limited, but used as usage range, hydroxyl equivalent is for example preferably below 5000g/eq, More preferably below 3000g/eq, especially preferably below 1000g/eq.
The resin containing phenolic hydroxyl group that is modified in present embodiment is referred to relative to the starting material for only using phenol as resin Matter and the phenolic resin that synthesizes, possess the resin of the structure that any part is changed, and intramolecular has the tree of phenolic hydroxyl group Fat.
For example, as the example of the modified resin containing phenolic hydroxyl group, can enumerate dimethylbenzene phenol-formaldehyde resin modified etc. makes phenol The resin for being reacted and being synthesized with the compound as modifying agent.
Also, as other examples of the modified resin containing phenolic hydroxyl group, can enumerate m-cresol resin, xylenol resin, Naphthol resin etc. uses the resin synthesized by the phenols beyond phenol.
Also, used as other examples of the modified resin containing phenolic hydroxyl group, can illustrate makes the phenols beyond phenol change with conduct The resin that the compound of property agent is reacted and synthesized.
Catalyst can be suitably used in the synthetic reaction of above-mentioned resin.
The organic compound with hydroxyl in this phenols refers to aromatic compound.In the present embodiment, phenols bag Include the organic compound of the functional group that so-called phenol and cresol etc. are provided with beyond 1 hydroxyl on phenyl ring.As phenols Concrete example, can for example enumerate following substances, but be not limited to this：Phenol；Orthoresol, metacresol, paracresol, xylenols Or the alkyl substituted benzene phenols such as p-t-butyl phenol；The aromatic series substituted benzene phenols such as 4-hydroxydiphenyl；Catechol or isophthalic two The dihydric phenol class such as phenol；Aphthols such as alpha-Naphthol or betanaphthol etc..
The compound as modifying agent is illustrated below.
The catalyst used in the case where the modified resin containing phenolic hydroxyl group is generated can enumerate following material.If will urge Agent rough classification, can enumerate two kinds of acid catalyst and base catalyst.
Specifically, as acid catalyst, following material can be enumerated, but is not limited to this：Hydrochloric acid, sulphuric acid, phosphoric acid or The inorganic acid catalysts such as phosphorous acid；The metallic catalysts such as lewis acid catalyst；Dithyl sulfate, oxalic acid or p-methyl benzenesulfonic acid etc. Organic acid catalyst；Zinc acetate etc..
Also, as base catalyst, following material can be enumerated, but be not limited to this：Sodium hydroxide, Lithium hydrate or hydrogen The base catalysts such as potassium oxide；The alkaline-earth metal catalysts such as calcium, magnesium or barium；The amine system catalyst such as ammonia；Zinc acetate.
When the modified resin containing phenolic hydroxyl group is generated, can be used alone a kind of catalyst, or also can simultaneously with two or more Catalyst.
In addition, in the case where phenolic resin is generated, catalyst reaction can be further used as desired.
The modified resin containing phenolic hydroxyl group of present embodiment is e.g. containing the change of the structure represented by following formulas (4) Compound.Wherein, in formula (4), P represents the structure containing phenolic hydroxyl group, and A and B is represented and constituted the modified tree containing phenolic hydroxyl group The arbitrary atom or atom group of the main chain of fat, X represents any aryl, and n is more than 1 integer.
The upper limit of the n in this formula (4) is not particularly limited, from the tree that secondary battery negative pole contains phenolic hydroxyl group with being modified From the viewpoint of the practicality of fat, preferred n is less than 1000 integer.
The modified resin containing phenolic hydroxyl group of present embodiment can contain following formulas (4) institute for a part for repetitives The resin of the structure of expression, alternatively following formulas (4) essentially become repetitives and continuous resin.
Specifically, formula (4) if in P be the structure containing phenolic hydroxyl group, then can illustrate benzene nucleus, naphthalene core, anthracene core Etc. generally known aryl, but it is not limited to these.
Specifically, the X in formula (4) can illustrate the generally known aryl such as benzene nucleus, naphthalene core, anthracene core, but not limit In these.
The modified resin containing phenolic hydroxyl group represented by formula (4) is due to multiple aromatic rings, and hydroxyl equivalent More than setting, thus as generate secondary cell material with carbon element initial substance and it is preferred that.
The modified resin containing phenolic hydroxyl group of present embodiment can for above-mentioned formula (4) in, especially following formula (5) institute tables The compound for showing.
(wherein, in formula (5), X1 to X4 separately represents the substituent group or hydrogen atom that benzene nucleus possesses.)
That is, in formula (5), the X in formula (4) is appointed as the benzene nucleus with X1 to X4.
The modified resin containing phenolic hydroxyl group represented by formula (5) due to being with multiple benzene skeletons, and hydroxyl equivalent It is more than setting, thus as generate secondary cell material with carbon element initial substance and it is preferred that.
The modified resin containing phenolic hydroxyl group represented by formula (5) has in the repetitives of resin and contains phenolic hydroxyl group Structure (P in formula (5)) and the above-mentioned structure containing phenolic hydroxyl group beyond benzene nucleus (hereinafter also referred to as benzene nucleus), hydroxyl Equivalent is more than 115g/eq.In addition, benzene nucleus contained in formula (4) refers to the carbon hexatomic ring with armaticity.
Being modified represented by formula (4) contains the resin of phenolic hydroxyl group due to having the structure containing phenolic hydroxyl group and benzene nucleus, Therefore possesses the benzene skeleton of more than 2 in the repetitives of the modified resin containing phenolic hydroxyl group.Therefore, present embodiment changes Property the resin containing phenolic hydroxyl group the preferred carbon containing class graphene-structured is easily formed in the operation burnt till and be carbonized Crystallite, as secondary battery negative pole material with carbon element initial substance and it is preferred that.
The modified resin containing phenolic hydroxyl group of present embodiment can be that a part for the repetitives of resin contains formula (5) The mode of the structure of represented regulation.
The benzene nucleus different from the structure containing phenolic hydroxyl group contained by above-mentioned repetitives has X1 to X4, and they are only respectively It is on the spot hydrogen or any substituent group.Also, (the especially adjacent any two of the position of substitution takes any two substituent group of X1 to X4 Dai Ji) can mutually be bonded and form circulus.
Hydrogen atom more than any one of the X1 to X4 in formula (5) can be respectively, but it is also former for hydrogen more than any one Son and other be any substituent group.Also, X1 to X4 can all identical substituent groups, replacement that also can be more than any two Base is for identical substituent group and other are different substituent groups.
X1 to X4 in formula (5) is not particularly limited, for example, can illustrate the substituent groups such as following radicals：Methyl, vinyl Or the alkyl such as pi-allyl；Amino；Vinyl；The aryl such as phenyl；Hydroxyl.By the repetitives of the resin containing phenolic hydroxyl group that is modified In contain these substituent groups, when being burnt till to the modified resin containing phenolic hydroxyl group and being generated material with carbon element, substituent group is temporary each other Shi Jianhe or substituent group become steric hindrance, thus can expect to suppress being drawn by the dehydrating condensation of hydroxyl in the structure containing phenolic hydroxyl group The crosslinking for rising.
A preferred example of the modified resin containing phenolic hydroxyl group of the present embodiment is appointing for the X1 to X4 in formula (5) More than one anticipate for methyl.
Its reason is, the resin containing phenolic hydroxyl group that is modified is burnt till and when being carbonized, as the X1 to X4 of methyl Any one substituent group that there is carbon with other reacted and contributed to forming the hexa-atomic ring skeleton of carbon.Thus, it is modified and contains phenol Property hydroxyl resin can generate with the structure containing phenolic hydroxyl group in formula (5) and with benzene nucleus side by side and containing from methyl Carbon carbon hexatomic ring material with carbon element.
X1 and X2 in above-mentioned formula (5) for example can be as shown in following formulas (6), 1 across benzene nucleus of X1 and X2 Carbon atom and be located at meta.In addition, in formula (6), X3 and X4 is hydrogen, and omits diagram.
It is as the modified of present embodiment that X1 and X2 in formula (5) is the modified resin containing phenolic hydroxyl group of methyl Resin containing phenolic hydroxyl group and one of preferred example.Now, X3 and X4 are, for example, hydrogen, but are not limited to this.
That is, the example of the preferred modified resin containing phenolic hydroxyl group in as present embodiment, during formula (5) can be enumerated X1 and X2 is methyl and two methyl are located at the molecular structure (with reference to formula (6)) of meta across 1 carbon atom.
Meta is configured at by methyl, during by the modified resin carbonation containing phenolic hydroxyl group, possesses the ring of the carbon contained by methyl Hexane is adjacent to phenyl ring and is formed, and expects to be consequently formed preferred class graphene-structured.
In the present embodiment as the preferred example of the modified resin containing phenolic hydroxyl group represented by formula (6), can Enumerate following resin.
For example, A and B be methylene, X1 and X2 for methyl the modified resin containing phenolic hydroxyl group as in present embodiment The modified resin containing phenolic hydroxyl group and it is preferred that.
Also, A is methylene, B be at least with the methylene that is bonded with the benzene nucleus shown in formula (6) and with the methylene The atom group of other benzene nucleus of bonding, X1 and X2 at least any one for methyl the modified resin containing phenolic hydroxyl group as this The modified resin containing phenolic hydroxyl group in embodiment and it is preferred that.
Also, A is methylene (the first methylene), B is at least have the methylene being bonded with the benzene nucleus shown in formula (6) (the second methylene) and other benzene nucleus being bonded with the methylene (the second methylene) and with replace B contained by it is above-mentioned its The atom group of the methyl (the first methyl) of the hydrogen of his benzene nucleus, and at least any one changing for methyl (the second methyl) of X1 and X2 Property the resin containing phenolic hydroxyl group as present embodiment in the modified resin containing phenolic hydroxyl group and it is preferred that.More specifically, example Methylene (second methylene) of the methyl (the first methyl) that above-mentioned other benzene nucleus as contained by above-mentioned B have contained by with B Bonding position replaces hydrogen for first at 6th clockwise.
Then, the A and B in mutual-through type (4) is illustrated.A and B in formula (4) be and the X (aryl) in formula (4) The arbitrary atom or atom group of bonding and the main chain of the modified resin containing phenolic hydroxyl group of composition.A and B can be identical atom or phase With atom group, alternatively different atom or different atom groups, also can any of which be atom, another be atom Group.
As above-mentioned atom, oxygen etc. can be enumerated, but be not limited to this.Also, as above-mentioned atom group, methylene can be enumerated The alkyl chains such as base (- CH2-), but this is not limited to, also can further have complicated molecular structure.
For example, in formula (4) can contain in A or the molecular structure of B different from the P shown in formula (4) containing phenol The structure of hydroxyl or the benzene nucleus different from the benzene nucleus shown in formula (4).Thus, by containing benzene skeleton in A or B, it is modified to this When resin containing phenolic hydroxyl group is burnt till and is carbonized, can expect to form better class graphene-structured.
As the example of the preferred specific structure of formula (4), chemical formula (7) as follows can be enumerated to chemical formula (10).But mutual-through type (4) is not limited in any way these concrete examples.N in chemical formula (7) to chemical formula (10) be respectively 1 with On integer, the upper limit is not particularly limited, from from the viewpoint of practicality, preferred n be less than 1000.
In order to generate the modified resin containing phenolic hydroxyl group represented by formula (4), for example, phenols can be made with following formulas (11) modifying agent represented by is reacted.Catalyst can be suitably used in the reaction.But formula (11) is not to being used to generate The modifying agent of the modified resin containing phenolic hydroxyl group of present embodiment is defined.
(wherein, in formula (11), C represents the atom containing the A in formula (4) or atom group, and D is represented containing in formula (4) B atom or atom group, X1 and X2 separately represents the substituent group or hydrogen atom that benzene nucleus possesses.)
Modifying agent represented by formula (11) has benzene nucleus and atom or atom group (C and D i.e. in formula (11)), The atom or atom group contain the atom that is bonded benzene nucleus with the phenols for being reacted or atom group (that is, A in formula (4) and B).Therefore, the modifying agent represented by formula (11) is made to carry out the modified resin containing phenolic hydroxyl group for reacting in weight with phenols Containing the benzene skeleton of more than 2 in multiple unit, and hydroxyl equivalent is more than 115g/eq.
As one of modified specific compound of resin containing phenolic hydroxyl group represented by formula (4), phenol can be enumerated Aralkyl resin.
Phenol aralkyl resin is to instigate above-mentioned phenols to carry out reaction with the aralkyl compound as modifying agent to give birth to Into resin.
The group that 1 hydrogen atom of alkyl is replaced by aryl such as phenyl is referred in this aralkyl.Above-mentioned aralkyl Compound refers to the compound with above-mentioned aralkyl.
Wherein, the compound that preferably 1 hydrogen atom of organic compound replaces with the phenyl for constituting aralkyl, and The aralkyl compound of para-position is located at by the phenyl, the alkyl of composition aralkyl and above-mentioned organic compound.Especially, more preferably The abovementioned alkyl of para-position and the molecular structure identical aralkyl compound of above-mentioned organic compound are located at by phenyl.As outstanding The concrete example of its preferred aralkyl compound, can enumerate terephthaldehyde's diethylene glycol dimethyl ether or p-divinyl benzene etc..
The phenol aralkyl resin generated by the reaction of above-mentioned preferred aralkyl compound and phenols is used as this reality Apply the modified resin containing phenolic hydroxyl group in mode and it is preferred that.
The modified resin containing phenolic hydroxyl group that making above-mentioned preferred aralkyl compound and phenols carries out reacting be In the repetitives of resin containing the benzene skeleton of more than 2 and hydroxyl equivalent for more than 115g/eq straight-chain resin, operation Property easily, and carry out carbonization and can provide battery behavior excellent material with carbon element by burning till.
The modified preferred phenol aralkyl resin of resin containing phenolic hydroxyl group in as present embodiment, e.g. makes phenol The modified resin containing phenolic hydroxyl group that class is reacted and obtained with terephthaldehyde's diethylene glycol dimethyl ether under acidic catalyst.As upper Acidic catalyst is stated, for example, can enumerate dithyl sulfate, but be not limited to this.
Also, as different modes, as present embodiment in the modified preferred phenol of resin containing phenolic hydroxyl group Aralkyl resin is, for example, the modified hydroxyl containing phenol for making phenols be reacted and be obtained under acidic catalyst with divinylbenzene The resin of base.As above-mentioned acidic catalyst, for example, p-methyl benzenesulfonic acid can be enumerated, but be not limited to this.
As one of modified different particular compound of resin containing phenolic hydroxyl group represented by formula (4), can enumerate Phenols and dimethylbenzene or dimethylbenzene modified compound is set to carry out the dimethylbenzene phenol-formaldehyde resin modified for reacting.
Dimethylbenzene phenol-formaldehyde resin modified is the benzene skeleton containing more than 2 and hydroxyl equivalent in the repetitives of resin For the resin of more than 115g/eq, can provide battery behavior excellent material with carbon element by burning till to carry out being carbonized.
Dimethylbenzene can be any one in o-Dimethylbenzene, meta-xylene or xylol.Also, dimethylbenzene modified compound Can be any one in o-Dimethylbenzene modified compound, meta-xylene modified compound or xylol modified compound.Diformazan Benzene modified compound is not particularly limited, for example, can enumerate multiple dimethylbenzene straight-chain is cross-linked into by methyl and/or ehter bond and Into compound.With regard to commercially available product, the dimethylbenzene modified compound (trade name of Fudow Co., Ltd.s manufacture can be illustrated： NIKANOL (registered trade mark)), but it is not limited to this.
According to the method for generally known novolak resin, also can by making phenol beyond monomer and the aldehydes such as formaldehyde Synthesized in the presence of acid or base catalyst, and resin of the synthesis modification containing phenolic hydroxyl group.
Hereinafter, with regard to for implementing mode of the invention, successively to secondary battery negative pole resin combination, negative pole carbon The detailed content of material, negative electrode active material, secondary battery negative pole and secondary cell is illustrated.
<Secondary battery negative pole resin combination>
The modified resin containing phenolic hydroxyl group of the present invention also can form secondary battery negative pole carbon materials by individually burning till Material, but secondary battery negative pole resin combination is constituted in the lump (hereinafter also referred to as with arbitrary additive sometimes according to needs Resin combination).
For example, the resin combination of the modified resin containing phenolic hydroxyl group containing the present invention and firming agent can be also prepared, and It is used as the material of secondary battery negative pole material with carbon element.Its reason is, when being carbonized, promotes modified to contain phenol being burnt till The heat cure of the resin of property hydroxyl.
The use level of the firming agent in resin combination is not particularly limited, such as relative to the modified tree containing phenolic hydroxyl group The mass parts of fat 100 are more than 0.1 mass parts below 50 mass parts.
The preparation method of resin combination is not particularly limited, and can be implemented by appropriate method.For example, can be by changing Property the resin containing phenolic hydroxyl group and the additive (1) that is properly added melt the method for mixing, (2) and be dissolved in solvent and mixing Method that method, (3) are pulverized and mixed etc. and prepare.
<Secondary battery negative pole material with carbon element>
Then, the secondary cell of the present invention is illustrated with material with carbon element.
The material with carbon element of the present invention is the material with carbon element generated using the modified resin containing phenolic hydroxyl group of the invention described above.
The material with carbon element of the present invention and the resin using the hydroxyl equivalent as novolak phenolics less than 115g/eq The material with carbon element for being generated is compared, and efficiency for charge-discharge is improved, and battery behavior is excellent.
The material with carbon element that especially the modified resin containing phenolic hydroxyl group represented by mutual-through type (4) is burnt till and is carbonized Efficiency for charge-discharge obtain good improvement.Think that its reason is, due to modified containing phenolic hydroxyl group as initial substance Resin repetitives in there is the benzene skeleton of more than 2, therefore the material with carbon element for being generated has containing class graphene-structured Preferred carbon crystallite.
As the optimal way of the present invention, the per unit volume that particle diameter distribution of the material with carbon element containing with good grounds number benchmark is obtained Surface area (the hereinafter also referred to as surface area of per unit volume) be 10000cm-1Above 16000cm-1The carbon of following scope Granule.
The lower limit of the surface area of above-mentioned per unit volume can further be set to 12000cm-1More than.Also, above-mentioned per unit The upper limit of the surface area of volume can further be set to 15500cm-1Below or 14000cm-1Below.
The material with carbon element of the present invention can serve as the material with carbon element of the materials'use of negative pole active substance.Containing per unit volume Surface area for above range carbon granule material with carbon element have at low ambient temperatures suppress secondary cell discharge and recharge when electricity The effect (hereinafter also referred to resistance inhibition) of resistance increase.
The manufacture method of the material with carbon element of the present invention is not particularly limited, for example can be by following manufacture method suitably Manufacture.
That is, material with carbon element of the invention can be made by the manufacture method with the first firing process and the second firing process Make.
Firing condition of maximum temperature when first firing process is to burn till less than 1000 DEG C contains phenolic hydroxyl group to modified Resin or the resin combination containing the modified resin containing phenolic hydroxyl group (be hereinafter sometimes referred to modified the resin containing phenolic hydroxyl group Deng) burnt till and generated the operation of material with carbon element precursor.
Maximum temperature when second firing process is to burn till is that the firing condition of more than 1000 DEG C of temperature burns to first Burnt till into the material with carbon element precursor generated in operation, thus generated the operation of material with carbon element.
Manufacture method by more than, can obtain the material with carbon element of the present invention, but the manufacture method is to manufacture the side of material with carbon element One example of method.The material with carbon element generated using the modified resin containing phenolic hydroxyl group of the present invention also can by with above-mentioned manufacture Other different manufacture methods of method and manufacture.
Hereinafter, the of the invention of the material with carbon element containing the modified resin containing phenolic hydroxyl group using the present invention etc. is born Pole active substance, the negative pole of the invention of the negative electrode active material containing the present invention and possess the of the invention secondary of the negative pole Battery is illustrated.
<Secondary battery negative pole active substance>
Then the secondary battery negative pole active substance of the present invention is illustrated.
The negative electrode active material of the present invention contains above-mentioned material with carbon element of the invention.As noted previously, as the carbon of the present invention Material realizes the improvement of efficiency for charge-discharge, therefore the efficiency for charge-discharge of the negative electrode active material of the invention containing the material with carbon element Also improved.
<Secondary battery negative pole and secondary cell>
Then, the secondary battery negative pole and secondary cell of the present invention are illustrated.
The negative pole of the present invention has the negative electrode active material layer containing above-mentioned negative electrode active material of the invention and stacking There is the negative electrode collector of the negative electrode active material layer.
The secondary cell of the present invention possesses negative pole, electrolyte and the anode of secondary cell of the present invention.
The negative pole of the present invention possesses the negative electrode active material layer of the negative electrode active material being improved containing efficiency for charge-discharge, Show excellent battery behavior.Therefore, the battery behavior for possessing the secondary cell of the invention of the negative pole of the present invention is excellent, can Expectation is used in various fields.
Hereinafter, the negative pole and the secondary cell of the invention for possessing the negative pole of the present invention are illustrated.Fig. 1 is to represent to contain There is an example of the lithium rechargeable battery of the material with carbon element generated using the modified resin containing phenolic hydroxyl group of the present invention Schematic diagram.
Fig. 1 is the schematic diagram of the lithium rechargeable battery 100 of an example of the secondary cell as the present invention.
Lithium rechargeable battery 100 is as shown in figure 1, have negative pole 10, positive pole 20, barrier film 30 and electrolyte 40.
Negative pole 10 is as shown in figure 1, have negative electrode active material layer 12 and negative electrode collector 14.
Negative electrode active material layer 12 is containing using the above-mentioned modified resin containing phenolic hydroxyl group of the invention as initial substance The material with carbon element of the invention for being generated.
Negative electrode collector 14 is not particularly limited, and can generally use known negative pole collector, for example, can use Copper Foil Or nickel foil etc..
More than, it is illustrated by taking the lithium rechargeable battery 100 of present embodiment as an example, but it is not precluded from using The secondary cell that the material with carbon element that the modified resin containing phenolic hydroxyl group of the present invention is generated is used for beyond lithium rechargeable battery Situation.The material with carbon element generated using the modified resin containing phenolic hydroxyl group of the present invention for example can also be used for the lithiums such as sodium ion from Secondary cell of the basic ion beyond son as chemical species.
Then, the 3rd aspect of the present invention is illustrated.With regard to basic with first method, second method Aspect identical Upper omission is recorded, and is illustrated centered on the aspect different from first method, second method.
The present inventor in order to improve material with carbon element in chemical species occlusion and release and studied, if find contain The phosphorus of prescribed limit and realize carbon dioxide less than setting adsorbance material with carbon element, then can solve above-mentioned problem, from And complete the present invention.
That is, although conventional material with carbon element suggests as mentioned above the hold-up by improving lithium ion containing phosphorus, and To making, the lithium ion of occlusion does not fully discharge and studies.
The present inventor is conceived to the carbon dioxide adsorption of material with carbon element in for the research for solving above-mentioned problem.It is known The big material with carbon element of the adsorbance of generally carbon dioxide, the occlusion of lithium ion is excellent.For example, in Japanese Unexamined Patent Publication 10-223226 There is the adsorbance of carbon dioxide disclosed in publication (patent documentation 3) for the use in electrode for secondary battery carbonaceous material of more than 10ml/g, And have as described below：The adsorbance of carbon dioxide is mixed for the lithium ion of the use in electrode for secondary battery carbonaceous material of below 10ml/g Miscellaneous amount is little and not preferred.
However, according to the research of the present inventor, it is known that although the adsorbance of carbon dioxide is the material with carbon element of more than 10ml/g The hold-up increase of lithium ion, but irreversible tendency is stronger.Its reason is still not clear, but speculates the lithium ion of institute's occlusion two There is clustering in the inside of the big material with carbon element of the adsorbance of carbonoxide, thus become to be difficult to be released.
Therefore, the present inventor is furtherd investigate, and as a result in the material with carbon element of the phosphorus containing prescribed limit, is generated generally It is considered as the undesirable carbon materials for showing the carbon dioxide adsorption less than 10ml/g from from the viewpoint of the occlusion of lithium ion Material., it is surprising that the material with carbon element is although the adsorbance of carbon dioxide is less than the occlusion of the chemical species such as 10ml/g, lithium ion But it is improved.Also, in the material with carbon element of the present invention, the release of the lithium ion of institute's occlusion is also improved, efficiency for charge-discharge Also it is excellent.That is, in material with carbon element of the invention, the phosphorus containing required scope and less than setting carbon dioxide adsorption this two Plant feature to interact, so as to the occlusion and release of chemical species are improved.
<Secondary battery negative pole material with carbon element>
Hereinafter, the mode of the material with carbon element to being used to implement the present invention is described in detail.In addition, with regard to present embodiment Explanation in, suitably illustrate so that lithium ion is as in the way of chemical species as an example, but this for illustrate, it is not excluded that this reality The material with carbon element occlusion for applying mode discharges the mode of other chemical species.
The secondary battery negative pole material with carbon element of present embodiment using carbon as main component, with more than 0.3 mass % 1.5 matter The scope of amount below % contains phosphorus, and the adsorbance of carbon dioxide is that per unit weight is less than 10ml/g.
In the material with carbon element of the present embodiment with this composition, the occlusion and release of the chemical species such as lithium ion are changed It is kind.That is, in the material with carbon element in present embodiment, the hold-up of the chemical species such as lithium ion is improved, and can fully be discharged The chemical species of institute's occlusion, therefore efficiency for charge-discharge is high.Accordingly, as constitute secondary battery negative pole material and it is preferred that, The battery behavior using the secondary battery negative pole of the material can be improved.
The material with carbon element of present embodiment is using carbon as main component.Although the so-called main component of here is not designated as accurately Numerical value, but the carbon atom preferably at least in the composition 100% of material with carbon element consists of more than 80%, more preferably 90% with On, especially preferably more than 95%.In addition, the material with carbon element of present embodiment is at least containing the carbon as main component and regulation model The phosphorus for enclosing, but it is not precluded from the situation containing the atom beyond them.
(content of phosphorus)
In the material with carbon element of present embodiment contained phosphorus relative to material with carbon element with more than 0.3 mass % 1.5 mass % below Scope contain.It is that more than 0.3 mass % the hold-up of lithium ion is significantly changed by the content of the phosphorus contained by material with carbon element It is kind.Also, the content for passing through the phosphorus contained by material with carbon element is below 1.5 mass %, can to improve the hold-up of lithium ion, and will be made Ratio of components for the carbon of the main component of material with carbon element is maintained higher.In the present invention, the content of phosphorus for example can be used by adjusting Suitably adjusted in additions of phosphate cpd such as the phosphate ester for generating material with carbon element etc..
In the present embodiment, the content of phosphorus for example can be using high-frequency induction coupled plasma (ICP) emission spectrum point Analysis apparatus are measured.
(adsorbance of carbon dioxide)
In the material with carbon element of present embodiment, the adsorbance of carbon dioxide is that per unit weight is less than 10ml/g, more preferably Below 5ml/g.It is above-mentioned numerical range by the adsorbance of carbon dioxide, the release of lithium ion is excellent.Its reason is still failed to understand Really, thus it is speculated that by the adsorbance of carbon dioxide be the numerical range, the clustering of the lithium ion of institute's occlusion can be prevented, is realized smooth Release.And, it is believed that the adsorbance of the carbon dioxide for generally illustrating in present embodiment for the occlusion of lithium ion not It is preferred that, but by the presence of the phosphorus contained by material with carbon element, even if also can improve under the numerical range of the adsorbance of the carbon dioxide The occlusion of lithium ion.
The lower limit of the adsorbance of the carbon dioxide of the material with carbon element of present embodiment is not particularly limited, such as preferred per unit Weight is more than 0.05ml/g, more preferably more than 0.1ml/g.Its reason is, if under the adsorbance of carbon dioxide is above-mentioned More than limit value, then it is difficult to hinder the occlusion of lithium ion, interacts with the effect containing phosphorus, can occlusion lithium ion well.
In the present embodiment, the adsorbance of carbon dioxide can use vacuum drier true to material with carbon element with 200 DEG C Used as sample is determined, determine device using known carbon dioxide adsorption is carried out material obtained from sky is dry more than 2 hours Determine.As CO 2 measuring device, for example, NIPPON BEL CO. can be enumerated, the gas absorption of LTD. manufactures determines dress Put (BELSORP-max).
In order that the carbon dioxide adsorption of material with carbon element is less than setting, and for example, the phosphorus used during to generating material with carbon element The condition more than any one such as the selection of the phosphate cpds such as acid esters, the selection of firming agent or curing catalysts or firing temperature It is adjusted.
(phosphorus or phosphorus compound contained by material with carbon element)
The material with carbon element of present embodiment contains the quilt detected by X-ray photoelectron spectroscopic analysis (hereinafter also referred to XPS) Phosphorus (hereinafter also referred to reducing phosphorus) or the compound containing phosphorus after reduction.Here, by the reduction phosphorus that XPS is detected and be able to will contain The compound for having phosphorus is referred to as target compound.
From from the viewpoint of the battery performance for improving material with carbon element, the material with carbon element of present embodiment is preferably with respect to above-mentioned target The composition 100% of compound, the triphenyl phosphine oxide ((C contained by target compound6H5)3P (=O)), triphenyl phasphine ((C6H5)3P) and gone back Each ratio of components of the phosphorus after original adds up to more than 50%, and the ratio of components of the phosphorus after being reduced is less than 13%.
Material with carbon element in present embodiment can be shown with the ratio of components of the reduction phosphorus on surface as less than 13% and more than 0% Write ground to exist.
It can be seen from the research of the present inventor, in the target compound contained by material with carbon element, detect substantial amounts of phosphorus and constitute The direct key (P-C keys) of the carbon of benzene nucleus and indirect key (P-O-C keys) that non-phosphorus is closed with the carbon for constituting benzene nucleus via oxygen key, and carbon materials The reduction phosphorus on the surface of material is not excessive, thus the high tendency of the battery performance with material with carbon element.This can be improved by this composition The reason for battery performance of the material with carbon element of embodiment, is still not clear, but speculates that these are constituted to preferred class graphite in material with carbon element The realization of alkene structure brings wholesome effect.In addition, in this manual " class graphene-structured " refers to that at least local has such as The structure of lower structure：Chip architecture with the structure same or like with the carbon hexagonal lattice structure that Graphene is shown, Or the stepped construction of the chip architecture lamination.
Target compound can be because different for generating the species or formation condition etc. of the initial substance of material with carbon element.Example Such as, as the material with carbon element recommended in present embodiment, can enumerate to containing phenolic resin and triphenyl phosphate ((C6H5O)3P(- O resin combination)) is burnt till generated material with carbon element, as the target compound detected by XPS in the material with carbon element, bag Containing following material.
[target compound 1] (C6H5O)3P (=O)
[target compound 2] (C6H5O)2P (=O) is (OH)
[target compound 3] (C6H5)2P (=O) is (OH)
[target compound 4] (C6H5)3P (=O)
[target compound 5] (C6H5)3P
[target compound 6] reduces phosphorus
The material with carbon element of present embodiment preferably with respect to these target compounds 1 to 6 total composition, target compound 4 to 6 it is each What is constituted adds up to more than 50%.
(ratio of components of oxygen and carbon)
The oxygen that the material with carbon element of present embodiment is preferably detected by X-ray photoelectron spectroscopic analysis (XPS) is constituted with carbon Than O/C more than the oxygen detected by composition analysis and the ratio of components O/C of carbon.
That is, the O conversion oxygen contents and C conversion carbon contents in the surface of material with carbon element is determined by XPS, their composition is obtained Compare O/C.Also, the O conversion oxygen total contents and C conversion total carbons in material with carbon element is determined by composition analysis, theirs are obtained Ratio of components O/C.As described above, it is preferred to the oxygen detected by XPS is more than the oxygen detected by composition analysis with the ratio of components O/C of carbon With the ratio of components O/C of carbon.
Speculate the feature according to above-mentioned oxygen and the ratio of components O/C of carbon, the presence ratio of carbon in the main body (inside) of material with carbon element Rate is high, forms preferred class graphene-structured.
(ratio of components of the surface of material with carbon element and the phosphorus of main body)
The ratio of components P of the phosphorus that the material with carbon element of present embodiment is preferably detected by X-ray photoelectron spectroscopic analysis (XPS) (XPS) more than the ratio of components P (COMP) of the phosphorus detected by composition analysis.
That is, the P conversion phosphorus contents in the surface of material with carbon element are determined by XPS.Also, determine material with carbon element by composition analysis In P conversion phosphorus total content.And their ratio of components is compared, preferably P (XPS)>P(COMP).
As described above, the battery of material with carbon element can be improved more than inside by the presence ratio of phosphorus on the surface for making material with carbon element Performance.Its reason is still not clear, thus it is speculated that can suitably play the effect of the occlusion for promoting the lithium ion in material with carbon element.
The particularly preferred P of the material with carbon element (XPS) of present embodiment>P (COMP) and P (COMP) is more than 0.Its reason is, Although ratio of components is worse than surface, in the inside of material with carbon element phosphorus is also significantly contained, thus can successfully occlusion lithium ion until The inside of material with carbon element.
In addition, the detection based on XPS in present embodiment can use known X-ray photoelectron spectroscopic analysis device, Specifically, the X-ray photoelectron spectroscopic analysis device ESCA-3400 of Shimadzu Scisakusho Ltd's manufacture can be for example used, But it is not limited to this.
Composition analysis refer to the analysis of the element contained by material with carbon element entirety in the present invention.Specific point of above-mentioned composition analysis Analysis method is not particularly limited, and can suitably select known method and implement.
For example, contained by material with carbon element carbon, hydrogen and nitrogen can be carried out quantitatively by Oxygen cycle burning, gas chromatography.Tool For body, burnt completely with about 850 DEG C of material with carbon elements for becoming sample, generate CO2Gas and H2O gases, and by gas chromatogram Method is carried out quantitatively to the carbon and hydrogen contained by these gases.Nitrogen is reduced after above-mentioned burning completely, and as N2Gas is same Ground is carried out quantitatively by gas chromatography.
Also, the oxygen contained by material with carbon element can be carried out quantitatively by adding thermal melting, non-dispersion infrared line absorption method.It is concrete and Speech, is heated with about 2500 DEG C under helium atmosphere to the material with carbon element for becoming sample, generates CO gases and CO2Gas, and lead to Cross non-dispersion infrared line absorption method is carried out quantitatively to the oxygen contained by these gases.
Also, the phosphorus contained by material with carbon element can be by ashing, acid melting, high-frequency induction coupled plasma optical emission spectrum analyses Method is carried out quantitatively.Specifically, after the material with carbon element for becoming sample is ashed so as to melt in hydrochloric acid, and by high-frequency induction Coupled plasma optical emission spectra methods are carried out quantitatively to the phosphorus contained by fused mass.
As the optimal way of the present invention, the per unit volume that particle diameter distribution of the material with carbon element containing with good grounds number benchmark is obtained Surface area (the hereinafter also referred to as surface area of per unit volume) be 10000cm-1Above 16000cm-1The carbon of following scope Granule.
The lower limit of the surface area of above-mentioned per unit volume can further be set to 12000cm-1More than.Also, above-mentioned per unit The upper limit of the surface area of volume can further be set to 15500cm-1Below or 14000cm-1Below.
The material with carbon element of the present invention can serve as the material with carbon element of the materials'use of negative pole active substance.Containing per unit volume Surface area for above range carbon granule material with carbon element have at low ambient temperatures suppress secondary cell discharge and recharge when electricity The effect (hereinafter also referred to resistance inhibition) of resistance increase.The original of resistance inhibition is played in the material with carbon element of aforesaid way Because being still not clear.However, the material with carbon element of which is with particle diameter, and moderately small and per unit volume surface area fully increases Mode is constituted.Thus it is speculated that the occlusion release efficiency of the lithium ion of the material with carbon element of which is high, even if at low ambient temperatures lithium from In the case that the action of son becomes slow, occlusion release also can be successfully carried out.In other words, thus it is speculated that the material with carbon element of which with Past material with carbon element is compared the surface area of the granule that can make the occlusion release areas as lithium ion and is significantly increased, and thus makes up for The reduction of the lithium ion mobility under low temperature environment simultaneously suppresses the increase of resistance.
<The manufacture of secondary battery negative pole material with carbon element>
Hereinafter, an example of the manufacture method of the material with carbon element of present embodiment is illustrated.According to described below Manufacture method (hereinafter also referred to as this manufacture method), can suitably manufacture the material with carbon element of present embodiment.But following institute This manufacture method recorded is not limited in any way to the manufacture method of the material with carbon element of the present invention.
(preparation of secondary battery negative pole resin combination)
First, the resin combination for manufacturing material with carbon element is prepared.
The resin combination that this manufacture method is used contains organic compound and phosphate cpd.
Organic compound：
Organic compound is not particularly limited, for example, can use the resin containing phenolic hydroxyl group and acenaphthylene or asphalt Deng oil based material.
Resin containing phenolic hydroxyl group is the material for being capable of synthetic, can correspond to used technical field variation Secondary cell, extend negative pole design degree of freedom.Consider that the resin containing phenolic hydroxyl group is used as the carbon in negative pole from the viewpoint The initial substance of material and it is preferred that.
In the present embodiment, the resin containing phenolic hydroxyl group refers to that intramolecular has the resin of phenolic hydroxyl group.This embodiment party The resin containing phenolic hydroxyl group in formula includes：Novolak phenolics or resol type phenol resin etc. are using phenol as starting Material and the resin that synthesizes；The tree that m-cresol resin, xylenol resin, naphthol resin etc. are synthesized using the phenols beyond phenol Fat；By in the presence of acid or base catalyst by phenol beyond the intramolecular that synthesizes of the aldehydes such as monomer and formaldehyde have The resin of phenolic hydroxyl group；Or being modified containing modifying agent contains the resin of phenolic hydroxyl group in above-mentioned resin.
For example, the above-mentioned compound containing phenolic hydroxyl group can by being reacted phenols and arbitrary compound of reaction and Synthesis.
Wherein, the hydroxyl equivalent with novolak phenolics as representative as 300g/eq below containing phenolic hydroxyl group Resin, its molecular structure is simplified and is readily synthesized, and is one of preferred example of initial substance as material with carbon element.
The little resin containing phenolic hydroxyl group of hydroxyl equivalent contains multiple hydroxyls in intramolecular, therefore is being used for material with carbon element carbon In the firing process of change, the hydroxyl is crosslinked in intramolecular and/or intermolecular dehydrating condensation, it is possible in the material with carbon element for being generated In preferred class graphene-structured growth it is hindered.In contrast, by the resin combination in the material for becoming material with carbon element Contain aftermentioned specific phosphate ester in thing, the dehydrating condensation of above-mentioned hydroxyl can be suppressed, and manufacture the occlusion release of lithium ion The material with carbon element of the high present embodiment of amount.
It is the resin containing phenolic hydroxyl group of below 300g/eq as hydroxyl equivalent, novolak type phenol tree can be enumerated Fat, resol type phenol resin contain the resin of phenolic hydroxyl group between phenols and phenols with reference to being modified for arbitrary modifying agent Deng, but it is not limited to this.
Here, hydroxyl equivalent refers to molecular weight of the resin containing phenolic hydroxyl group relative to 1 hydroxyl.The measure of hydroxyl equivalent Can carry out according to the neutralization titration of the defineds of JIS K 0070 (1992).
In addition, in this manual, novolak phenolics are referred to makes under an acid catalysis above-mentioned phenols and first The phenolic resin that aldehyde is reacted and synthesized.In addition, in this manual, resol type phenol resin is referred to be made under base catalyst The phenolic resin that above-mentioned phenols is reacted and synthesized with formaldehyde.
Generally, hydroxyl equivalent it is less (for example hydroxyl equivalent be below 200g/eq, be further below 150g/eq, especially It is below 120g/eq), it is more preferred from from the viewpoint of ease of manufacturing and manufacturing cost, can expect as secondary battery cathode The use of pole material.By containing the little tree containing phenolic hydroxyl group of this hydroxyl equivalent in the resin combination of the present invention Fat, substantially can be used as to provide the initial substance of the material with carbon element for showing excellent battery behavior.
In this manufacture method, the resin containing phenolic hydroxyl group includes being closed by making phenols be reacted with compound of reaction Into resin.Catalyst can be as needed used in the synthesis of the resin containing phenolic hydroxyl group.Here, phenols refers to aromatic series The organic compound with hydroxyl, not only comprising so-called phenol, and is provided with 1 comprising cresol etc. on phenyl ring in compound The organic compound of the functional group beyond individual hydroxyl.Above-mentioned compound of reaction not only includes formaldehyde, and comprising can synthesize The modifier compound of the modified resin containing phenolic hydroxyl group.
As the concrete example of phenols, for example, can enumerate phenol；Orthoresol, metacresol, paracresol, xylenols or to uncle The alkyl-substituted phenols class such as butylphenol；The aromatic series substituted benzene phenols such as 4-hydroxydiphenyl；The binary such as catechol or resorcinol Phenols；Aphthols such as alpha-Naphthol or betanaphthol etc., but it is not limited to these materials.
Phosphate cpd：
In order that containing phosphorus in the material with carbon element for generating, in the resin combination that this manufacture method is used phosphorylation is contained Compound.
The phosphate cpd that this manufacture method is used is not particularly limited, for example can be using phosphoric acid or phosphorus pentoxide The smaller phosphate cpd of equimolecular quantity or aftermentioned specific phosphate cpd.From the oxidation provided contained by above-mentioned target compound Adding up to from the viewpoint of more than 50% material with carbon element for each ratio of components of triphenyl phasphine, triphenyl phasphine and phosphorus atoms, preferably uses phosphorus Acid esters particularly preferably uses the phosphate ester for possessing more than 1 phenyl as phosphate cpd.
In addition, the resin containing phenolic hydroxyl group from below using hydroxyl equivalent as 300g/eq is used as initial substance, and suppress by From the viewpoint of the crosslinking that the dehydrating condensation of hydroxyl causes, make to exceed containing boiling temperature or heat decomposition temperature in resin combination This contains the phosphate ester or phosphoric acid derivatives that self condense temperature of the resin of phenolic hydroxyl group.Thus, in order to by resin combination Thing is carbonized and in the case of burning till to it, the moment for self condensing is started (that is, containing phenolic hydroxyl group in the resin containing phenolic hydroxyl group The hydroxyl that possesses of resin carry out dehydrating condensation and crosslink the stage of reaction), not boiling or undecomposed phosphorus can be made Acid esters etc. is present in response system.Thus, hydrogen bonding is carried out with the hydroxyl of the resin containing phenolic hydroxyl group by making phosphate ester etc. Deng or covered, and reduce the reactivity of the hydroxyl, suppress the crosslinking caused by dehydrating condensation, can expect to avoid hindering carbon Crystal structure growth situation.
In addition, in this manual, it is so-called to self condense, as long as no special instructions, then refer to that the resin containing phenolic hydroxyl group is had Some phenolic hydroxyl group are in intramolecular and/or intermolecular carry out dehydrating condensation.
The use level of the phosphate ester contained by resin combination that this manufacture method is used etc. is not particularly limited, for example, Preferably with respect to the mass parts of resin 100 containing phenolic hydroxyl group, phosphate ester is contained with the scope below more than 3 mass parts 15 mass parts Or phosphoric acid derivatives.Thus, it is possible to make generated material with carbon element be contained with the scope below more than 0.3 mass % 1.5 mass % Phosphorus.
The phosphate ester contained by resin combination or phosphoric acid derivatives that this manufacture method is used preferably selects fusing point and is less than The phosphate ester or phosphoric acid derivatives that self condense temperature of the resin containing phenolic hydroxyl group.
Thus, in the operation burnt till to resin combination and generated material with carbon element, can be in the tree containing phenolic hydroxyl group The hydroxyls dehydrate of fat is condensed and starts to start the melting of phosphate ester etc. before being crosslinked, and can improve the phosphate ester in resin combination Deng dispersibility.It is well dispersed within resin combination by making phosphate ester etc., can be made relative to the tree containing phenolic hydroxyl group Significantly few phosphate ester of fat content etc. effectively acts on the suppression of the hydroxyl crosslinking in the resin containing phenolic hydroxyl group.In addition, The above-mentioned carbon material with carbon element high with the ratio of components of the Direct Bonding (P-C keys) of phosphorus can be generated.
For example, when the hydroxyl of novolak phenolics is in about 300 DEG C of beginning dehydrating condensations, preferably phosphoric acid ester etc. Fusing point is less than 300 DEG C.For example, consider that preferably using triphenyl phosphate, fusing point that fusing point is more than 48.5 DEG C is from above-mentioned viewpoint The aromatic condensation ester of more than 92 DEG C of above-mentioned chemical formula (1), fusing point are about 200 DEG C polyphosphoric acid etc..
In addition, in this manufacture method, the fusing point of the fusing point of phosphate ester etc. and the resin containing phenolic hydroxyl group is referred to by differential The temperature of the summit of the endothermic peak that scanning amount thermal analysis system (hereinafter also referred to DSC) is analyzed.
Additive：
Any additive can also be contained as needed in the resin combination that this manufacture method is used.For example, originally The resin combination that manufacture method is used can also contain firming agent.Its reason is that firming agent can promote containing phenolic hydroxyl group Resin heat cure.
Firming agent is not particularly limited, and is determined according to appropriate with the combination of the resin containing phenolic hydroxyl group for being used. For example, in the case where the resin containing phenolic hydroxyl group contained by resin combination is novolak phenolics, can be appropriate Ground uses hexamethylenetetramine, resol type phenol resin or polyacetals etc..In addition, contained by resin combination containing phenolic hydroxyl group Resin be resol type phenol resin in the case of, it is possible to use hexamethylenetetramine etc..
The use level of the firming agent in resin combination is not particularly limited, such as relative to the resin containing phenolic hydroxyl group 100 mass parts are more than 0.1 mass parts below 50 mass parts.Even if not using firming agent, contained phenolic aldehyde in resin combination Varnish-type phenolic resin can also solidify in the operation that the resin combination is burnt till and is carbonized, but it is also possible to not show The scope for writing the growth of the crystal structure for hindering that generated material with carbon element is burnt till to resin combination contains firming agent.Example Such as, firming agent is not particularly limited relative to the content of novolak phenolics, can be relative to novolak type phenol The mass parts of resin 100 contain firming agent with the scope below more than 0.1 mass parts 5 mass parts.
As the additive beyond firming agent, for example, organic acid, mineral acid, nitrogen-containing compound, oxygen-containing chemical combination can be enumerated Thing, aromatic compound, nonferrous metal atom etc..These additives can be according to the species of the resin for being used or character etc. Using a kind of or be applied in combination two or more.
(burning till for resin combination)
Then, below to this manufacture method that the resin combination for preparing as described above burns till and generates material with carbon element is entered Row explanation.Specifically, to using hydroxyl equivalent for the resin containing phenolic hydroxyl group of below 300g/eq and containing boiling temperature or Heat decomposition temperature exceedes the phosphate ester for self condensing temperature or the resin combination of phosphoric acid derivatives of the resin containing phenolic hydroxyl group The example of the material with carbon element of manufacture present embodiment is illustrated.
This manufacture method for example has the first firing process and the second firing process.
Firing condition of maximum temperature when first firing process is to burn till less than 1000 DEG C is used secondary battery negative pole Resin combination is burnt till and is generated the operation of material with carbon element precursor.
Maximum temperature when second firing process is to burn till is that the firing condition of more than 1000 DEG C of temperature burns to first Burnt till into the material with carbon element precursor generated in operation, thus generated the operation of material with carbon element.
First firing process and the second firing process can continuously be implemented, it is also possible to be performed separately.
As the example of the mode for being performed separately the first operation and the second operation, for example can the first firing process with The pulverizing process that the material with carbon element precursor that will be obtained by the first firing process is crushed is set between the second firing process.From making second From the viewpoint of the thermal process of the material with carbon element precursor in firing process becomes uniform, above-mentioned pulverizing process is preferable to carry out.Above-mentioned powder The particle diameter of the ground product of the material with carbon element precursor obtained in broken operation is not particularly limited, and is less than more than 1 μm 20 μm, more preferably Less than more than 5 μm 15 μm.By more than the lower limit that makes the particle diameter of above-mentioned ground product be above-mentioned numerical range, the operation of ground product Property it is good, and the phosphorus contained by phosphate ester etc. can be made significantly to remain in the material with carbon element being ultimately formed.In addition, on by making The particle diameter for stating ground product is below the higher limit of above-mentioned numerical range, can well to realize the material with carbon element in the second firing process Thermal process homogenization.
The particle diameter of above-mentioned ground product refers to particle diameter (D50, average grain during 50% accumulation in the cumulative distribution of volume reference Footpath).
In addition, the pulverization conditions in by adjusting above-mentioned pulverizing process, can manufacture containing the per unit for preferred scope The material with carbon element of the surface area of volume or the carbon granule of the mean square radius of gyration.
Breaking method in above-mentioned pulverizing process is not particularly limited, for example, can use arbitrary reducing mechanism.As Above-mentioned reducing mechanism, can enumerate the impingements such as ball mill apparatus, vibrator device, rod mill device, bead mill apparatus Reducing mechanism；Or the air flow crushing device such as airswept mill device, aeropulverizer device, dry type air flow crushing device, but do not limit In these.In pulverization process, these devices can use one or more, or can be carried out repeatedly by a kind of device Crush and use.In addition, in pulverization process, in addition to these devices, it is also possible to be suitably classified using sieve etc., separately Outward, it is also possible to using the reducing mechanism with grading function.
This manufacture method includes melting stage and material with carbon element precursor generation phase in the first firing process.
The above-mentioned melting stage is by the resin containing phenolic hydroxyl group and phosphate ester contained by secondary battery negative pole resin combination Or phosphoric acid derivatives melt.
Above-mentioned material with carbon element precursor generation phase forms the crystallite containing defat and/or the preferred carbon of class graphene-structured.
The carbon manufacture method of present embodiment is preferably spread out in the phosphorus compound or phosphoric acid for making to be melted by the above-mentioned melting stage Before biology boiling or decomposition, heated by the resin containing phenolic hydroxyl group to being melted using the melting stage and generated carbon materials Material precursor.
In the first firing process, in order to realize above-mentioned melting stage and above-mentioned material with carbon element precursor generation phase, for example, make Exceed room temperature with the fusing point of the resin containing phenolic hydroxyl group and phosphate ester contained by resin combination etc. and the tree for less than 250 DEG C Oil/fat composition.Thus, it is possible to contain the self shrinking of the resin of phenolic hydroxyl group in for the firing process of carbide resin compositionss Run jointly and make before beginning the melting such as the resin containing phenolic hydroxyl group and phosphate ester (melting the stage).
By further under high temperature (such as less than more than 300 DEG C 800 DEG C) to existing through the melting stage containing phenol The resin combination of the resin and phosphate ester of hydroxyl etc. is burnt till, can by containing phenolic hydroxyl group resin formation contain defat and The crystallite of the preferred carbon of class graphene-structured, forms material with carbon element precursor.In this manufacture method, in material with carbon element precursor rank is generated There is boiling or the phosphate ester before thermal decomposition etc. in section, therefore the hydroxyl of the resin containing phenolic hydroxyl group can be suppressed to enter by dehydrating condensation The situation of row crosslinking.Result, it is believed that the crystal structure of the material with carbon element precursor for being generated is the occlusion of the chemical species such as lithium ion releasing The established structure of the excellent crystallite of exoergic power or the structure formed for the crystallite.
In this manufacture method, the above-mentioned melting stage and material with carbon element precursor generation phase can be in the first firing process It is middle independent and after the melting stage is fully completed start material with carbon element precursor generation phase mode or melt the stage second half section with Any one in the mode that the front half section of material with carbon element precursor generation phase is overlapped.
In the first firing process, melt the stage and material with carbon element precursor generation phase can be by the tree containing phenolic hydroxyl group The reduction or expansion of the volume of fat and phosphate ester etc. is measured and judges.That is, will pass through to burn till in the first firing process to make The thermal melting such as the resin containing phenolic hydroxyl group and phosphate ester and stage that volume is reduced tendency are referred to as the melting stage.In addition, will be The volume of the resin containing phenolic hydroxyl group reduced because of melting in the first firing process shows that the stage of expansion is referred to as material with carbon element Precursor generation phase.
Above-mentioned the first firing process and the gas atmosphere of the second firing process is not particularly limited, for example, can not live Carry out under bold and vigorous gas atmosphere.As above-mentioned inactive gas, nitrogen, argon, helium etc. can be enumerated.In these, particularly preferably Nitrogen.
The gas atmosphere of the first firing process and the second firing process can be the same or different.
The conditions such as programming rate, firing temperature, firing time in the first firing process and the second firing process can be Making the characteristic of the predetermined negative pole for using generated material with carbon element becomes optkmal characteristics and is suitably adjusted.
Material with carbon element manufacture method by more than, it is possible to obtain secondary battery negative pole material with carbon element.By this manufacture method The charge/discharge capacity and efficiency for charge-discharge of manufactured material with carbon element is improved, and battery behavior is excellent.
The negative pole active matter that secondary battery negative pole is used can serve as by the material with carbon element manufactured by present embodiment Matter.
In addition, the manufacture method of the secondary battery negative pole material with carbon element of the present invention discussed above is to manufacture this embodiment party One example of the method for the material with carbon element of formula, it is not excluded that manufacture the situation of the material with carbon element by other manufacture methods.
Hereinafter, to the material with carbon element containing the present invention negative pole active substance of the invention, possess containing negative pole work The secondary battery negative pole of the invention of the negative pole active material layer of property material and possesses the present invention of the secondary battery negative pole Secondary cell illustrate.
<Negative pole active substance>
The secondary battery negative pole active substance of the present invention contains above-mentioned secondary battery negative pole material with carbon element of the invention. Excellent material with carbon element of the invention, the negative pole of the present invention are discharged by the occlusion containing the alkali metal ion such as lithium ion or sodium ion The charging capacity and efficiency for charge-discharge of negative pole can be well favorably improved with active substance.Negative pole active substance in the present invention Referring to being capable of occlusion and the material for discharging the chemical species for becoming carrier in secondary battery negative pole.Above-mentioned chemical species for example exist Lithium ion or sodium ion etc. can be enumerated in alkali metal ion secondary cell.
Hereinafter, the negative pole of the resin combination containing the present invention is illustrated with active substance.
So-called negative pole active substance is being capable of occlusion and release alkali metal in the secondary cells such as alkali metal-ion battery The material of the chemical species such as ion (such as lithium ion or sodium ion).Illustrated negative pole is referred to active substance in this specification Material containing the material with carbon element generated using the resin combination of the present invention.
Negative pole active substance can substantially only by the present invention material with carbon element constitute, but it is also possible to also containing with the carbon materials The different material of material.As this material, for example, silicon, silicon monoxide, other graphite materials etc. can be enumerated usually as negative Pole material and known material.
Particle diameter (mean diameter) when in the cumulative distribution of the volume reference of the graphite material for being used 50% is accumulated It is preferred that less than more than 2 μm 50 μm, more preferably less than more than 5 μm 30 μm.
<Secondary battery negative pole and secondary cell>
Hereinafter, the secondary battery negative pole and the secondary cell of the invention for possessing the secondary battery negative pole of the present invention are carried out Explanation.
The secondary battery negative pole of the present invention is that have containing above-mentioned secondary battery negative pole active substance of the invention Secondary battery negative pole active material layer and it is laminated with the negative pole collector of secondary battery negative pole active material layer and constitutes 's.
In addition, the secondary cell of the present invention is that possess above-mentioned secondary battery negative pole of the invention, electrolyte and secondary electricity Pond positive pole and constitute.
The negative pole of the present invention is constituted using the negative pole active substance of the present invention, thus charging capacity and efficiency for charge-discharge It is excellent.In addition, the secondary cell of the invention for possessing the negative pole of the present invention reflects the charging capacity and efficiency for charge-discharge of negative pole Raising, show excellent battery performance.
Embodiment
Hereinafter, examples and comparative examples of the present invention are illustrated.But the present invention is not limited to reality shown below Apply example and comparative example.In addition, in embodiment, " part " expression " mass parts ", " % " expression " quality % ".
(synthesis of the resin containing phenolic hydroxyl group)
The resin containing phenolic hydroxyl group that embodiment or comparative example are used is synthesized in the following manner first.
(synthesis of novolak phenolics)
3 parts of 100 parts of phenol, 64.5 parts of 37% formalin and oxalic acid are loaded possess blender and cooling tube three mouthfuls In flask, after reacting 3 hours at 100 DEG C, heat up and be dehydrated and obtain 90 parts of novolak phenolics.According to JIS K 0070 (1992) neutralization titration determines the hydroxyl equivalent of the novolak phenolics being obtained as described above, as a result for 105g/eq。
(synthesis of resol type phenol resin)
1 part of 100 parts of phenol, 55 parts of paraformaldehyde and zinc acetate are loaded the there-necked flask for possessing blender and cooling tube In, it is dehydrated after reacting 3 hours at 100 DEG C, afterwards its ripening is made under 100 DEG C, the reaction condition of 2 hours, obtain solid-state 90 parts of resol type phenol resin.The resol type being obtained as described above is determined according to the neutralization titration of JIS K 0070 (1992) The hydroxyl equivalent of phenolic resin, is as a result 105g/eq.
(synthesis of dimethylbenzene modified novolac resin)
Using 100 parts of phenolic resin, as diformazan benzene series resin 70 parts of NIKANOL H (manufacture of Fudow Co., Ltd.s) and 25% 1 part of sulphuric acid is fitted in the there-necked flask for possessing blender and cooling tube, and 2 hours have been reacted at a reflux temperature.Then by Secondary 48 parts of 37% Formalin aqueous solution of addition, and reacted 2 hours.Afterwards, add calcium hydroxide to be neutralized, and it is de- to heat up Water, obtains 160 parts of dimethylbenzene phenol-formaldehyde resin modified.
Worked as with the hydroxyl that method similarly to Example 1 determines the dimethylbenzene phenol-formaldehyde resin modified being obtained as described above Amount, is as a result 155g/eq.
<Embodiment 1>
Relative to 100 parts of novolak phenolics being obtained as described above, using vibrator by tricresyl phosphate (DAIHACHI CHEMICAL INDUSTRY CO., LTD. are manufactured phenyl ester, trade name：TPP) 10 parts and 3 parts of hexamethylenetetramine Crush and mix, obtain resin combination.The resin combination being obtained as described above is set to into embodiment 1.
In a nitrogen atmosphere, the resin combination of embodiment 1 is carried out from room temperature with 100 DEG C/h of programming rate Heat up, after reaching 550 DEG C, state will be burnt till and kept for 1.5 hours and carried out carbonization treatment (the first firing process).Afterwards, it is real Pulverizing process is applied, material with carbon element precursor is obtained.
In a nitrogen atmosphere, above-mentioned material with carbon element precursor is burnt till from room temperature with 100 DEG C/h of programming rate, After reaching 1200 DEG C, state will be burnt till and kept for 2 hours and carried out carbonization treatment (the second firing process).With thus obtained carbon Material is used as the material with carbon element of embodiment 1.
In addition, the pulverization conditions of the above-mentioned pulverizing process in embodiment 1 are described below.Embodiment 2～9 and comparative example 1 Also pulverizing process has been carried out between the first firing process and the second firing process under pulverization conditions described later.
<Embodiment 2>
The triphenyl phosphate that embodiment 1 is used is changed to into aromatic condensation phosphate ester (DAIHACHI CHEMICAL INDUSTRY CO., LTD. are manufactured, trade name：PX-200) 10 parts, in addition, with same material and same method system Resin combination is obtained for resin combination.The resin combination being obtained as described above is set to into embodiment 2.
In addition to using embodiment 2, in the method same with the method for generating the material with carbon element of above-described embodiment 1 carbon materials are generated Material, as the material with carbon element of embodiment 2.
<Embodiment 3>
Relative to 100 parts of the resol type phenol resin being obtained as described above, using vibrator by triphenyl phosphate (DAIHACHI CHEMICAL INDUSTRY CO., LTD. are manufactured, trade name：TPP) crush and mix and set for 10 parts Oil/fat composition.The resin combination being obtained as described above is set to into embodiment 3.
In addition to the resin combination using embodiment 3, same with the generation method of the material with carbon element of the above embodiments 1 Under conditions of implement the first firing process and the second firing process and carried out carbonization treatment.Using thus obtained material with carbon element as The material with carbon element of embodiment 3.
<Embodiment 4>
In addition to not using firming agent, resin combination is prepared in the mode same with the above embodiments 1, be set to reality Apply example 4.
In addition to the resin combination using embodiment 4, with same with the generation method of the material with carbon element of the above embodiments 1 Mode generate material with carbon element, and using the material with carbon element as the material with carbon element of embodiment 4.
<Embodiment 5>
Relative to 100 parts of the dimethylbenzene modified novolac resin being obtained as described above, using vibrator by phosphorus (DAIHACHI CHEMICAL INDUSTRY CO., LTD. are manufactured triphenyl phosphate ester, trade name：TPP) 10 parts crush and mix and Obtain resin combination.The resin combination being obtained as described above is set to into embodiment 5.
In addition to the resin combination using embodiment 5, same with the generation method of the material with carbon element of the above embodiments 1 Under conditions of implement the first firing process and the second firing process and carried out carbonization treatment.Using thus obtained material with carbon element as The material with carbon element of embodiment 5.
<Embodiment 6>
Resin combination is prepared in the way of similarly to Example 1, by the temperature in the second firing process from 1200 DEG C of changes More 1100 DEG C, in addition, implement first under conditions of same with the generation method of the material with carbon element of the above embodiments 1 and burn till Operation and the second firing process and carried out carbonization treatment.Using thus obtained material with carbon element as the material with carbon element of embodiment 6.
<Embodiment 7>
Prepare resin combination in the way of similarly to Example 1, and be changed to as described later with the powder of embodiment 1 The different pulverization conditions of fringe part, it is in addition, real under conditions of same with the generation method of the material with carbon element of the above embodiments 1 Apply the first firing process and the second firing process and carry out carbonization treatment.Using thus obtained material with carbon element as the carbon of embodiment 7 Material.
<Embodiment 8>
Prepare resin combination in the way of similarly to Example 1, and be changed to as described later with the powder of embodiment 1 The different pulverization conditions of fringe part, it is in addition, real under conditions of same with the generation method of the material with carbon element of the above embodiments 1 Apply the first firing process and the second firing process and carry out carbonization treatment.Using thus obtained material with carbon element as the carbon of embodiment 8 Material.
<Embodiment 9>
Relative to the biphenyl aralkyl resin as commercially available product, (Nippon Kayaku Co., Ltd.s manufacture, trade name： Kayahard GPH-103, hydroxyl equivalent 228) 100 parts, using vibrator by triphenyl phosphate (DAIHACHI CHEMICAL INDUSTRY CO., LTD. are manufactured, trade name：TPP) 10 parts, 3 parts of hexamethylenetetramine crushes and mixes and obtain Obtained resin combination.The resin combination being obtained as described above is set to into embodiment 9.The phosphorus content in embodiment 9 is calculated, As a result it is 0.84%.
In addition to the resin combination using embodiment 9, in the condition same with the generation method of the material with carbon element of embodiment 1 It is lower to implement the first firing process and the second firing process and carried out carbonization treatment.Using thus obtained material with carbon element as embodiment 9 material with carbon elements.
<Comparative example 1>
Using the novolak phenolics being obtained as described above as comparative example 1.
In a nitrogen atmosphere, using 100 DEG C/h of programming rate by as the novolak phenolics of comparative example 1 100 parts are heated up from room temperature, after reaching 550 DEG C, will be burnt till state and are kept for 1.5 hours and carried out carbonization treatment (first Firing process).Afterwards, implement pulverizing process, obtain material with carbon element precursor.
In a nitrogen atmosphere, above-mentioned material with carbon element precursor is burnt till from room temperature with 100 DEG C/h of programming rate, After reaching 1200 DEG C, state will be burnt till and kept for 2 hours and carried out carbonization treatment (the second firing process).With thus obtained carbon Material is used as the material with carbon element of comparative example 1.
Calculate each embodiment and the phosphorus content contained by each comparative example and be shown in table 1.
In addition, the pulverizing process in each embodiment and each comparative example is using the burned material obtained by the first firing process, Carry out under following pulverization conditions.By the carbon precursor obtained by pulverizing process for the second firing process.
Embodiment 1：The intermedium implemented the first firing process and obtain is placed naturally and is cooled to room temperature, using ball mill Reducing mechanism is put in the container of the alumina balls 900g of the alumina balls 5000g and φ 10mm equipped with φ 15mm and is processed, Obtain crushing intermedium.Then the sieve for above-mentioned crushing intermedium being passed through into 75 μm of mesh, removes big particle, is crushed Thing (material with carbon element precursor).
Embodiment 2 is to embodiment 6：Pulverizing process is carried out under conditions of similarly to Example 1, ground product (carbon is obtained Material precursor).
Embodiment 7：The intermedium implemented the first firing process and obtain is placed naturally and is cooled to room temperature, using Cyclone mill Machine reducing mechanism, in powder body quantity delivered 50g/min, air quantity 0.5m3Wheel speed 15000rpm, the 2nd crushing are crushed in/min, the 1st Crushed under conditions of wheel speed 15000rpm and obtained crushing intermedium.Then, above-mentioned crushing intermedium is passed through The sieve that 75 μm of mesh, removes big particle, obtains ground product (material with carbon element precursor).
Embodiment 8：The intermedium implemented the first firing process and obtain is placed naturally and is cooled to room temperature, using Cyclone mill Machine reducing mechanism, in powder body quantity delivered 30g/min, air quantity 0.8m3Wheel speed 13000rpm, the 2nd crushing are crushed in/min, the 1st Crushed under conditions of wheel speed 13000rpm and obtained crushing intermedium.Then, above-mentioned crushing intermedium is passed through The sieve that 75 μm of mesh, removes big particle, obtains ground product (material with carbon element precursor).
Comparative example 1：Pulverizing process is carried out under conditions of similarly to Example 1, ground product (material with carbon element precursor) is obtained.
In addition, the reducing mechanism that above-mentioned pulverization process is used is for example following.
Ball mill reducing mechanism has used rotary ball mill (offer of 1 grade of formula-B, IRIE SHOKAI Co., Ltd.).
Airswept mill reducing mechanism used Dry-crusher (150BMW type airswept mills, SHIZUOKA PLANT CO., LTD. manufacture).
[measure of true specific gravity]
For each embodiment material with carbon element and comparative example material with carbon element that are obtained as described above, by using the true specific gravity of butanol Assay method determines true specific gravity.Measurement result is shown in into table 1.
[measure of surface area]
Using particle size distribution device (particle size distribution device LA-920, HORIBA, Ltd. are manufactured), by following The particle diameter distribution of the number benchmark of each embodiment material with carbon element of step measurements and comparative example material with carbon element.
By the material with carbon element 20mg being obtained as described above, dilution be for about 1wt% surfactant (Tween 20, Kishida Chemical Co., Ltd.s manufacture) 1ml and distilled water about 5ml is fitted in a polyethylene can, is positioned in In ultrasonic washing unit, while mixing 1 minute using polyethylene suction pipe (polyspuit), while applying ultrasound wave it is disperseed, And obtain dispersion.By above-mentioned dispersion for above-mentioned particle size distribution device, enter under the setting of relative index of refraction 1.5 The measure of particle diameter distribution is gone.
Using the data obtained by above-mentioned particle size distribution measuring, per unit volume is calculated according to above-mentioned mathematical expression (1) Surface area.The value for being calculated is shown in into table 1.
[calculating of the mean square radius of gyration]
Using the data obtained by above-mentioned particle size distribution measuring, each embodiment is calculated according to above-mentioned mathematical expression (2) The mean square radius of gyration of material with carbon element and comparative example material with carbon element.The value for being calculated is shown in into table 1.
<The making of half-cell type lithium rechargeable battery>
(making of negative pole)
In order to evaluate the battery behavior of each embodiment material with carbon element being obtained as described above and comparative example material with carbon element, The negative pole using each material with carbon element has been made as described below.
Relative to each embodiment material with carbon element and comparative example material with carbon element each 100%, coordinated as binding agent using 3% ratio SBR styrene butadiene rubberses, using 1.5% ratio coordinate as viscosifier carboxymethyl cellulose, with 2% ratio coordinate As the acetylene black of conductive material, and add appropriate pure water and be diluted mixing, obtain the negative pole mixture of pulp-like.
With the copper that every secondary amounts identical mode is coated 10 μm of thickness by the negative pole mixture of the pulp-like of above-mentioned acquisition On paper tinsel (collector), with 110 DEG C 1 hour is vacuum dried.Then, the thickness that 60 μm are compressed and molded into by roll squeezer is obtained Copper Foil be punched to regulation shape, made diameter 13mm, the thickness of electrode active material layer (part in addition to collector) For 50 μm of discoid lithium ion secondary battery cathode.
(making of working electrode)
As working electrode, the lithium metal of thickness 1mm is prepared.
(preparation of electrolyte)
Hexafluoro is dissolved in the mixed liquor (volume ratio 3: 7) of ethylene carbonate and diethyl carbonate with the concentration of 1 mol/L Lithium phosphate, is prepared for electrolyte.
(making of lithium rechargeable battery)
Using the negative pole, working electrode, the electrolyte that are obtained as described above, lithium ion secondary electricity has been made as described below Pond.
Successively by negative pole, barrier film (polypropylene perforated membrane：25 μm of thickness), working electrode be configured at Hohsen Corp. systems The assigned position of the dual electrode cell made, injects electrolyte, has made lithium rechargeable battery.
[first charge-discharge characteristic evaluation]
Using the half-cell type lithium rechargeable battery for making as described above, battery behavior is have rated as described below.
Temperature of the measurement is set to into 25 DEG C, electric current density when charging is set to into 25mA/g carries out constant-current charge, reaches from current potential To from the moment of 0V, keep 0V and carry out constant-voltage charge, will charge to the electricity till electric current density becomes 2.5mA/g as first Secondary charging capacity.
Then, electric current density during electric discharge is set to into 25mA/g, carries out constant-current discharge, the moment of 2.5V is reached with current potential Electricity is used as initial discharge capacity.
As shown in following mathematical expressions (3), the value that initial discharge capacity is obtained divided by primary charging capacity is multiplied by 100 and counts Calculate first efficiency for charge-discharge.In addition, the result of first charge-discharge characteristic evaluation is shown in into table 1.
In addition, in the first charge-discharge characteristic is evaluated, " charging " is referred to by applied voltage, makes lithium ion from by metal The working electrode that lithium is constituted is to the negative pole movement constituted using material with carbon element.In addition, " electric discharge " refers to lithium ion from using carbon materials Phenomenon of the negative pole expected and constitute to the working electrode movement being made up of lithium metal.
First efficiency for charge-discharge (%)=[initial discharge capacity (mAh/g)/primary charging capacity (mAh/g)] × 100 (3)
<The making of full cell type Li-ion secondary cell>
In order to evaluate the battery behavior under the low temperature environment of the embodiment being obtained as described above and comparative example, system Full cell type Li-ion secondary cell is made.
Manufacture method is except the working electrode in the manufacture method of above-mentioned half-cell type lithium rechargeable battery is changed Beyond for positive pole, carry out in the same way.
As positive pole, using using LiCoO2 is as active substance and is coated positive pole made on collector, make For the collector of positive pole, adopt using the single-layer sheet of aluminium foil, (Pionics Co., Ltd. manufactures, trade name：Pioxcel C- 100) the discoid collector of diameter 12mm is formed as.
[low temperature environment test]
Using the full cell type Li-ion secondary cell for making as described above, it is determined as described below.
Temperature of the measurement is set to into 25 DEG C, electric current density when charging is set to into 25mA/g carries out constant-current charge, reaches from current potential To from the moment of 4.2V, keep 4.2V and carry out constant-voltage charge, charge to till electric current density reaches 2.5mA/g, then, will put Electric current density when electric is set to 25mA/g, carries out constant-current discharge, is discharged to till current potential reaches 2.5V.And then in same condition Under charge and discharge, implement the discharge and recharges of total 5 circulations and carried out burin-in process.
After burin-in process, under 25 DEG C of temperature environment each lithium rechargeable battery is charged to the constant current of 0.2C 4.2V, afterwards, 0.02C is decayed to the constant-voltage charge of 4.2V to current value.Then, discharged with the constant current of 0.2C, with into Mode for SOC (State of Charge) 50% is adjusted, and places 1 hour at 25 DEG C.Then, by each lithium ion two Primary cell is placed 1 hour under -20 DEG C of temperature environment, and following " low temperature environment charge and discharge electric treatment " have been carried out into 3 circulations.
That is, with regard to low temperature environment discharge process, lithium rechargeable battery is arranged under -20 DEG C of temperature environment, to Voltage when rated current value charges 10 seconds is measured, after then placing 10 minutes, to only discharging 10 with rated current value Second when voltage be measured, afterwards place 10 minutes.Specifically, above-mentioned rated current value is to be recycled to the 3rd from the 1st Individual circulation is followed successively by 1/3C, 0.5C, 1C.In above-mentioned low temperature environment discharge process, upper voltage limit is set to into 4.2V, is rationed the power supply by under Pressure is set to 2.5V.
In addition, here " 1C " refers to the electric current density terminated with electric discharge in 1 hour.
With regard to above-mentioned low temperature environment discharge process, current value is drawn in transverse axis, in the longitudinal axis charge or discharge in 10 seconds are drawn Voltage afterwards, D.C. resistance (DC- when obtaining the charging in battery according to the absolute value of the slope of its near linear and during electric discharge IR), and according to its value low temperature environment characteristic is evaluated as described below.DC-IR is low to refer to that resistance is little, and output characteristics is good It is good.
D.C. resistance when D.C. resistance during charging is 195 below Ω and/or discharges is 215 below Ω ... ◎
D.C. resistance during charging more than 195 Ω and for 210 below Ω and electric discharge when D.C. resistance more than 215 Ω and For 220 below Ω ... zero
D.C. resistance during charging is more than D.C. resistance when 210 Ω and/or electric discharge more than 220 Ω ... Δs
[High temperature storage characteristic evaluation]
Using the full cell type Li-ion secondary cell of each embodiment and comparative example for making as described above, such as it is following that Sample is evaluated High temperature storage characteristic.
Temperature of the measurement is set to into 25 DEG C, electric current density when charging is set to into 25mA/g carries out constant-current charge, reaches from current potential To from the moment of 4.2V, keep 4.2V and carry out constant-voltage charge, charge to till electric current density reaches 2.5mA/g, then, will put Electric current density when electric is set to 25mA/g, carries out constant-current discharge, is discharged to current potential and reaches 2.5V, in this, as 1 circulation.Further Charge and discharge under identical condition, implement the discharge and recharge of total 5 circulations and carried out burin-in process.Above-mentioned old During change is processed, the discharge capacity (discharge capacity I) during the electric discharge circulated to the 5th is determined.
Using the full cell type Li-ion secondary cell of Jing burin-in process as described above, electric current density is set to into 25mA/g Constant-current charge is carried out, from the moment that current potential reaches 4.2V, 4.2V is further kept and is carried out constant-voltage charge, charge to electric current close Till degree reaches 2.5mA/g, the lithium rechargeable battery that SOC is adjusted to 100% is prepared.
By the lithium rechargeable battery being obtained as described above 1 week certainly in temperature is adjusted to 60 DEG C of drying machine, such as It is following the discharge capacity of the lithium rechargeable battery after keeping is confirmed like that.
That is, using the lithium rechargeable battery after keeping, it is charged and discharges with the current value of 0.2C, in this, as 1 Individual circulation, implements the discharge and recharge of total 3 circulations.Discharge capacity (discharge capacity II) during the electric discharge circulated to the 3rd is entered Measure is gone.
As shown in following mathematical expressions (4), the discharge capacity (electric discharge of the 3rd circulation of the lithium rechargeable battery after keeping Capacity II) divided by the discharge capacity (discharge capacity I) of the 5th circulation during burin-in process, the value of acquisition is multiplied by 100, with thus The value of acquisition is evaluated as " High temperature storage characteristic ".
High temperature storage characteristic (%)=[discharge capacity II (mAh/g)/discharge capacity I (mAh/g)] × 100 (4)
The High temperature storage characteristic of each embodiment and comparative example is shown in into table 1.
[life characteristics at high temperature evaluation]
Using with above-mentioned High temperature storage characteristic evaluation in the same method of burin-in process carried out burin-in process and The each embodiment for obtaining and the full cell type Li-ion secondary cell of comparative example, are carried out as described below to life characteristics at high temperature Evaluate.
That is, after burin-in process, under 55 DEG C of temperature environment, each lithium rechargeable battery is charged with the constant current of 1C Until 4.2V, afterwards, is decayed to after 0.02C with the constant-voltage charge of 4.2V to current value, under 55 DEG C of temperature environment 30 are kept Minute.Then, with the constant-current discharge of 1C to 2.5V, kept for 30 minutes under 55 DEG C of temperature environment, in this, as 1 circulation. The discharge capacity (discharge capacity III) of the lithium rechargeable battery during electric discharge circulated to above-mentioned 1st is determined.
Then, the discharge and recharge of 99 circulations is implemented under conditions of as described above, filling for total 100 circulations is implemented Electric discharge.Discharge capacity (discharge capacity IV) during the electric discharge circulated to the 100th is measured, and has carried out " life characteristics at high temperature Evaluate ".Specifically, as shown in following mathematical expressions (5), the discharge capacity (discharge capacity IV) of the 100th circulation is divided by the 1st The discharge capacity (discharge capacity III) of circulation and the value that obtains is multiplied by 100, using thus obtained value as " life characteristics at high temperature " Evaluated.
Life characteristics at high temperature (%)=[discharge capacity IV (mAh/g)/discharge capacity III (mAh/g)] × 100 (5)
The life characteristics at high temperature of each embodiment and comparative example is shown in into table 1.
[the decomposition evaluation of the lithium rechargeable battery after experiment of high-temperature load]
Each embodiment for evaluating above-mentioned Jing life characteristics at high temperature under the environment below -60 DEG C of dew point and comparative example Lithium rechargeable battery decomposes, and visually confirms that lithium is separated out.
Specifically, each embodiment of 5 Jing life characteristics at high temperature evaluations and the lithium ion secondary of comparative example are prepared respectively Battery, each lithium rechargeable battery is decomposed, the lithium rechargeable battery to confirming lithium precipitation in exposed negative terminal surface Number evaluated.
In each embodiment and comparative example, lithium precipitation will be confirmed in 5 lithium rechargeable batteries in negative terminal surface The number of lithium rechargeable battery is shown in table 1.
As shown in table 1, if firing condition identical embodiment 1 is compared to embodiment 5 with comparative example 1, each reality Apply example and show the higher primary charging capacity of numerical value.In addition, each embodiment shows following situation：Primary charging capacity increases Initial discharge capacity also increases while big, and the lithium ion of institute's occlusion is reversibly discharged.As a result, embodiment 1 to Embodiment 5 is compared with comparative example 1, and efficiency for charge-discharge is higher.
In addition, also confirming the raising of battery behavior in embodiment 9.
Using novolak phenolics as the embodiment 1 of resin containing phenolic hydroxyl group, embodiment 2, embodiment 4 to Embodiment 6 significantly shows the improvement of efficiency for charge-discharge.
The surface area of the per unit volume of the material with carbon element of embodiment 1 to 7 is 10000cm2/cm3Above 16000cm2/cm3 Scope above, shows good low-temperature characteristics.Wherein, the surface area of per unit volume is 12000cm2/cm3Reality above Apply example 1 and show especially excellent low-temperature characteristics to the material with carbon element of embodiment 6.
The mean square radius of gyration of the material with carbon element of embodiment 3 and embodiment 7 is contained in 1 μm24 μm of the above2In the range of, can prevent The deterioration of the self discharge under hot environment, can expect to show the good coating to collector in addition.
Embodiment 1, embodiment 2, embodiment 4, embodiment 6 are 1.5g/cm to the true specific gravity of the material with carbon element of embodiment 83 Above 1.7g/cm3Following scope.Thus, the value stabilization of the charge/discharge capacity of the secondary battery negative pole for being constituted using these, The life characteristic for contributing to secondary cell can be expected in addition.
According to the High temperature storage characteristic evaluation using each embodiment and the lithium rechargeable battery of comparative example, show More than 80% high High temperature storage characteristic.The High temperature storage characteristic of especially embodiment is more than 85%, even if on 60 DEG C of left sides In the case of taking care of at a high temperature of the right side, also showing that can maintain the discharge capacity before keeping with very high ratio.According to this As a result suggest, even if the secondary battery negative pole material with carbon element of the invention contained by negative pole is in high temperature environments higher charging State, it is also possible to maintain carbon structure well.Speculate by maintaining the carbon structure, the self discharge of lithium of the occlusion in the material with carbon element Become to be difficult to produce with the formation of the overlay film of negative terminal surface, therefore, it is possible to remain of the invention under hot environment with high level The lithium occlusion release of secondary battery negative pole.
In addition, according to the life characteristics at high temperature evaluation using each embodiment and the lithium rechargeable battery of comparative example, showing More than 80% high High temperature storage characteristic is shown.The life characteristics at high temperature of especially embodiment is more than 85%, even if 55 DEG C or so at a high temperature of in the case of Reusability, also showing that can maintain discharge capacity with very high ratio.Thus it is dark Illustrate, in high temperature environments cycle characteristics is excellent for the negative pole of the secondary battery negative pole material with carbon element containing the present invention.
In addition, decompose the lithium rechargeable battery of each embodiment and comparative example after life characteristics at high temperature is evaluated, as a result The precipitation to lithium unconfirmed on negative pole of the lithium rechargeable battery of embodiment.On the other hand, the lithium ion secondary of comparative example Battery confirms lithium on negative pole and separates out with 20% ratio (specifically 5 in 1).Also implied according to the result Go out, even if the secondary battery negative pole material with carbon element of the invention contained by negative pole is in high temperature environments in the case of Reusability, The structure of carbon structure and negative plate can well be maintained.Speculate the structure by maintaining the carbon structure and negative plate, the present invention Lithium of the negative pole in high temperature occlusion release in its resistance variations can be mitigated with high level, as a result, the precipitation of lithium is received To suppression.
<Embodiment 10>
0.1 part of 100 parts of phenol, 100 parts of terephthaldehyde's diethylene glycol dimethyl ether and dithyl sulfate are loaded and possesses blender and cold But in the there-necked flask of pipe, less than 160 DEG C of scope carries out the dehydration of 3 hours more than 140 DEG C, and addition calcium hydroxide enters Neutralization is gone.Afterwards, intensification dehydration is carried out, obtains the phenol aralkyl resin 120 as the modified resin containing phenolic hydroxyl group Part.
The phenol aralkyl resin being obtained as described above according to the neutralization titration measure of JIS K 0070 (1992) Hydroxyl equivalent, is as a result 175g/eq.
In a nitrogen atmosphere, with 100 DEG C/h of programming rate by the phenol aralkyl resin being obtained as described above from Room temperature rises and is heated up, and after reaching 550 DEG C, state of burning till keeps having carried out within 1.5 hours carbonization treatment (the first firing process). Afterwards, implement pulverizing process, obtain material with carbon element precursor.
By the material with carbon element precursor 204g being obtained as described above to become thickness as thin as possible in the way of in furnace volume Extend in the heat-treatment furnace of 24L (long 40cm, width 30cm, high 20cm) and stand, in a nitrogen atmosphere, with 100 DEG C/h of liter Warm speed is burnt till from room temperature and after being reached 1200 DEG C, state of burning till keeps having carried out within 2 hours carbonization treatment that (second burns Into operation).Embodiment 10 will be set to by secondary cell material with carbon element achieved above.
In addition, the pulverization conditions of the above-mentioned pulverizing process in embodiment 10 are described below.Other embodiment and comparative example Also pulverizing process has been carried out between the first firing process and the second firing process under pulverization conditions described later.
<Embodiment 11>
Using 100 parts of phenolic resin, as diformazan benzene series resin 70 parts of NIKANOL H (manufacture of Fudow Co., Ltd.s) and 25% 1 part of sulphuric acid is fitted in the there-necked flask for possessing blender and cooling tube, reacts 2 hours at a reflux temperature.Then gradually Add 48 parts of 37% Formalin aqueous solution, and react 2 hours.Afterwards, add calcium hydroxide to be neutralized, and the dehydration that heats up, from And obtain 160 parts of the dimethylbenzene phenol-formaldehyde resin modified as the modified resin containing phenolic hydroxyl group.
Worked as with the hydroxyl that method similarly to Example 10 determines the dimethylbenzene phenol-formaldehyde resin modified being obtained as described above Amount, is as a result 155g/eq.
In addition to using the dimethylbenzene phenol-formaldehyde resin modified being obtained as described above, with same with the above embodiments 10 Mode implement the first firing process and the second firing process, carry out carbonization treatment.To be used by secondary cell achieved above Material with carbon element is set to embodiment 11.
<Comparative example 2>
3 parts of 100 parts of phenol, 64.5 parts of 37% formalin and oxalic acid are loaded possess blender and cooling tube three mouthfuls In flask, after being reacted 3 hours with 100 DEG C, heat up dehydration, obtains 90 parts of novolak phenolics.
Worked as with the hydroxyl that method similarly to Example 10 determines the novolak phenolics being obtained as described above Amount, is as a result 105g/eq.
In addition to using the novolak phenolics being obtained as described above, with same with the above embodiments 10 Mode implement the first firing process and the second firing process, carried out carbonization treatment.By by secondary cell achieved above Comparative example 2 is set to material with carbon element.
<Comparative example 3>
To the 100 portions of addition triphenyl phosphates 10 of novolak phenolics obtained in the mode same with comparative example 2 Part, 3 parts of hexamethylenetetramine, in addition, the first firing process and the are implemented in the mode same with the above embodiments 10 Two firing process, have carried out carbonization treatment.Comparative example 3 will be set to by secondary cell material with carbon element achieved above.
In addition, the pulverizing process in each embodiment and each comparative example is using the burned material obtained by the first firing process, Carry out under following pulverization conditions.By the carbon precursor obtained by pulverizing process for the second firing process.
Embodiment 10：The intermedium implemented the first firing process and obtain is placed naturally and is cooled to room temperature, using ball milling Machine reducing mechanism is put in the container of the alumina balls 900g of the alumina balls 5000g and φ 10mm equipped with φ 15mm to be located Reason, obtains crushing intermedium.Then the sieve for above-mentioned crushing intermedium being passed through into 75 μm of mesh, removes big particle, obtains Ground product (material with carbon element precursor).
Embodiment 11：Pulverizing process is carried out under conditions of similarly to Example 10, ground product is obtained (before material with carbon element Body).
Comparative example 2：Pulverizing process is carried out under conditions of similarly to Example 10, ground product is obtained (before material with carbon element Body).
Comparative example 3：The intermedium implemented the first firing process and obtain is placed naturally and is cooled to room temperature, using Cyclone mill Machine reducing mechanism, in powder body quantity delivered 50g/min, air quantity 0.5m3Wheel speed 15000rpm, the 2nd crushing are crushed in/min, the 1st Crushed under conditions of wheel speed 15000rpm and obtained crushing intermedium.Then, above-mentioned crushing intermedium is passed through The sieve that 75 μm of mesh, removes big particle, obtains ground product (material with carbon element precursor).
In addition, the reducing mechanism that above-mentioned pulverization process is used is for example following.
Ball mill reducing mechanism has used rotary ball mill (offer of 1 grade of formula-B, IRIE SHOKAI Co., Ltd.).
Airswept mill reducing mechanism used Dry-crusher (150BMW type airswept mills, SHIZUOKA PLANT CO., LTD. manufacture).
[measure of surface area]
The measure of surface area is carried out in the same manner as above.The value of calculating is shown in into table 2.
<The making of half-cell type lithium rechargeable battery>
The making of half-cell type lithium rechargeable battery is carried out in the same manner as above.
[first charge-discharge characteristic evaluation]
Using the half-cell type lithium rechargeable battery for making as described above, by changing condition determination as described below Two kinds of evaluation methodologys battery behavior is evaluated.
In addition, in the first charge-discharge characteristic is evaluated, " charging " is referred to by applied voltage, makes lithium ion from by metal The working electrode that lithium is constituted is to the negative pole movement constituted using material with carbon element.Also, " electric discharge " refers to lithium ion from using carbon materials Phenomenon of the negative pole expected and constitute to the working electrode movement being made up of lithium metal.
(battery behavior evaluates 1)
Temperature of the measurement is set to into 25 DEG C, electric current density when charging is set to into 25mA/g carries out constant-current charge, reaches from current potential To from the moment of 0V, keep 0V and carry out constant-voltage charge, will charge to the electricity till electric current density becomes 2.5mA/g as first Secondary charging capacity.
Then, electric current density during electric discharge is set to into 25mA/g, carries out constant-current discharge, the moment of 2.5V is reached with current potential Electricity is used as initial discharge capacity.
As shown in following mathematical expressions (2), the value that initial discharge capacity is obtained divided by primary charging capacity is multiplied by 100 and counts Let it pass first efficiency for charge-discharge.In addition, the result of first charge-discharge characteristic evaluation is shown in into table 2.
First efficiency for charge-discharge (%)=[initial discharge capacity (mAh/g)/primary charging capacity (mAh/g)] × 100 (2)
(battery behavior evaluates 2)
Temperature of the measurement is set to into 25 DEG C, electric current density when charging is set to into 40mA/g carries out constant-current charge, reaches from current potential To from the moment of 0V, keep 0V and carry out constant-voltage charge, will charge to the electricity till electric current density becomes 4.0mA/g as first Secondary charging capacity.
Then, electric current density during electric discharge is set to into 4.0mA/g carries out constant-current discharge, and current potential is reached the moment of 1.5V Electricity is used as initial discharge capacity.
Using above-mentioned mathematical expression (2), the first efficiency for charge-discharge that battery behavior is evaluated in 2 is calculated.In addition, will be first The result of charge-discharge characteristic evaluation is shown in table 2.
<The making of full cell type Li-ion secondary cell>
The making of full cell type Li-ion secondary cell is carried out in the same manner as above.
[low temperature environment test]
Low temperature environment test is carried out in the same manner as above.
With regard to above-mentioned low temperature environment discharge process, current value is drawn in transverse axis, in the longitudinal axis charge or discharge in 10 seconds are drawn Voltage afterwards, D.C. resistance (DC- when obtaining the charging in battery according to the absolute value of the slope of its near linear and during electric discharge IR), and according to the value low temperature environment characteristic is evaluated as described below.DC-IR is low to refer to that resistance is little, and output characteristics is good It is good.
D.C. resistance when D.C. resistance during charging is 195 below Ω and/or discharges is 215 below Ω ... ◎
D.C. resistance during charging more than 195 Ω and for 210 below Ω and discharge when D.C. resistance is more than 215 Ω and is 220 below Ω ... zero
D.C. resistance during charging is more than D.C. resistance when 210 Ω and/or electric discharge more than 220 Ω ... Δs
As shown in table 2, embodiment 10, embodiment 11 be compared with comparative example 2, during battery behavior under two conditions is evaluated Confirm the improvement of efficiency for charge-discharge.Embodiment 10, embodiment 11 are also significantly confirmed in the higher evaluation 2 of electric current fills The improvement of discharging efficiency, show the secondary battery negative pole of the present invention also can suitably be applied with the modified resin containing phenolic hydroxyl group In high current equipment.
Also, also show that appropriate value, and charge and discharge using the charge/discharge capacity of the embodiment 10 of phenol aralkyl resin Electrical efficiency is high, and showing can provide the negative pole for possessing the battery performance for obtaining balance.
Also, it is notable using the improvement that efficiency for charge-discharge is confirmed in the embodiment 11 of dimethylbenzene phenol-formaldehyde resin modified.
The surface area of the per unit volume of the material with carbon element of each embodiment is 10000cm2/cm3Above 16000cm2/cm3With On scope, show especially excellent low-temperature characteristics.Comparative example 3 makes condition due to adding additive when material with carbon element is generated Optimize, therefore the efficiency for charge-discharge in battery behavior evaluation 1,2 increases compared with comparative example 2, but in low-temperature characteristics evaluation Aspect does not obtain excellent evaluation.In contrast, embodiment shows preferably in efficiency for charge-discharge and low-temperature characteristics evaluation Evaluation, show under normal temperature environment and low temperature environment obtain balance battery performance.
<The synthesis of the resin containing phenolic hydroxyl group>
First, the novolak phenolics that embodiment or comparative example are used have been synthesized as described below.
3 parts of 100 parts of phenol, 64.5 parts of 37% formalin and oxalic acid are loaded possess blender and cooling tube three mouthfuls In flask, after reacting 3 hours with 100 DEG C, intensification dehydration is carried out, and obtain 90 parts of novolak phenolics.According to JIS The neutralization titration of K 0070 (1992) determines the hydroxyl equivalent of the novolak phenolics being obtained as described above, as a result For 105g/eq.
<Embodiment 12>
Relative to 100 parts of novolak phenolics being obtained as described above, using vibrator by tricresyl phosphate (Daihachi Chemical Industry Co., Ltd. manufactures phenyl ester, trade name：TPP) crush and mix with 3 parts of hexamethylenetetramine for 10 parts, and obtain Obtained resin combination.
In a nitrogen atmosphere, the resin combination of above-mentioned acquisition is carried out from room temperature with 100 DEG C/h of programming rate Heat up, after reaching 550 DEG C, state of burning till keeps having carried out within 1.5 hours carbonization treatment (the first firing process).Afterwards, implement Pulverizing process, and obtain material with carbon element precursor.
In a nitrogen atmosphere, above-mentioned material with carbon element precursor is burnt till from room temperature with 100 DEG C/h of programming rate, After reaching 1200 DEG C, state of burning till keeps having carried out within 2 hours carbonization treatment (the second firing process).With thus obtained carbon materials Material is used as embodiment 12.
In addition, the pulverization conditions of the above-mentioned pulverizing process in embodiment 12 are described below.Other embodiment and comparative example Also pulverizing process has been carried out between the first firing process and the second firing process under pulverization conditions described later.
<Embodiment 13>
Except the use level of triphenyl phosphate is changed in addition to 5 parts, give birth in the method same with the above embodiments 12 Into material with carbon element, as embodiment 13.
<Embodiment 14>
In the second firing process, 1200 DEG C of the retention time for burning till state is changed to into 4 hours, in addition, with The method same with the above embodiments 12 generates material with carbon element, as embodiment 14.
<Embodiment 15>
Resin combination is prepared in the way of similarly to Example 12, the crushing with embodiment 12 is changed to as described later The different pulverization conditions of condition, in addition, implement the first firing process and second under conditions of similarly to Example 12 Firing process.Using thus obtained material with carbon element as embodiment 15.
<Comparative example 4>
In a nitrogen atmosphere, with 100 DEG C/h of programming rate by the novolak type phenol tree being obtained as described above 100 parts of fat is heated up from room temperature, and after reaching 550 DEG C, state of burning till keeps having carried out carbonization treatment (first in 1.5 hours Firing process).Afterwards, implement pulverizing process, and obtain material with carbon element precursor.
In a nitrogen atmosphere, above-mentioned material with carbon element precursor is burnt till from room temperature with 100 DEG C/h of programming rate, After reaching 1200 DEG C, state of burning till keeps having carried out within 2 hours carbonization treatment (the second firing process).With thus obtained carbon materials Material is used as comparative example 4.
<Comparative example 5>
Relative to 100 parts of novolak phenolics, using 5 parts of 5 parts of triphenyl phosphate and hexamethylenetetramine, pass through Vibrator is pulverized and mixed and obtains resin combination.
Replace 100 parts of the novolak phenolics that comparative example 4 is used using above-mentioned resin combination, except this with Outward, material with carbon element is generated by the method same with above-mentioned comparative example 4, as comparative example 5.
In addition, the pulverizing process in each embodiment and each comparative example is using the burned material obtained by the first firing process, Carry out under following pulverization conditions.The carbon precursor obtained by pulverizing process is fed to into the second firing process.
Embodiment 12：The intermedium implemented the first firing process and obtain is placed naturally and is cooled to room temperature, using ball milling Machine reducing mechanism, is put in the container of the alumina balls 900g of the alumina balls 5000g and φ 10mm equipped with φ 15mm and is located Reason, and obtain crushing intermedium.Then, the sieve for above-mentioned crushing intermedium being passed through into 75 μm of mesh, removes big particle, so as to Obtain ground product (material with carbon element precursor).
Embodiment 13：Carry out pulverizing process under conditions of similarly to Example 12, and obtain ground product (before material with carbon element Body).
Embodiment 14：The intermedium implemented the first firing process and obtain is placed naturally and is cooled to room temperature, using whirlwind Pulverizing crushing device, in powder body quantity delivered 30g/min, air quantity 0.8m3/ min, first crush wheel speed 13000rpm, the second powder Crushed and obtained crushing intermedium under conditions of leaf cutting wheel rotating speed 13000rpm.Then, above-mentioned crushing intermedium is led to The sieve of 75 μm of mesh is crossed, big particle is removed, so as to obtain ground product (material with carbon element precursor).
Embodiment 15：The intermedium implemented the first firing process and obtain is placed naturally and is cooled to room temperature, using whirlwind Pulverizing crushing device, in powder body quantity delivered 50g/min, air quantity 0.5m3/ min, first crush wheel speed 15000rpm, the second powder Crushed and obtained crushing intermedium under conditions of leaf cutting wheel rotating speed 15000rpm.Then, above-mentioned crushing intermedium is led to The sieve of 75 μm of mesh is crossed, big particle is removed, so as to obtain ground product (material with carbon element precursor).
Comparative example 4 and comparative example 5：Pulverizing process is carried out under conditions of similarly to Example 12, and obtains ground product (material with carbon element precursor).
In addition, the reducing mechanism used in above-mentioned pulverization process is for example following.
Ball mill reducing mechanism has used rotary ball mill (offer of 1 grade of formula-B, IRIE SHOKAI Co., Ltd.).
Airswept mill reducing mechanism used Dry-crusher (150BMW type airswept mills, SHIZUOKA PLANT CO., LTD. manufacture).
[material with carbon element evaluation]
(phosphorus content)
The each embodiment being obtained as described above and each comparative example are dissolved in hydrochloric acid respectively and prepare sample, using height Frequency inductively coupled plasma (ICP) emission spectrographic analysis device has been carried out quantitatively to the phosphorus contained by the sample.By quantitative result It is shown in table 3.
(carbon dioxide adsorption)
Respectively each embodiment being obtained as described above and each comparative example are fed to into gas absorption and determine device (NIPPON BEL CO., LTD. are manufactured, BELSORP-max), the adsorbance of the carbon dioxide in material with carbon element is determined.Examination will be determined Sample 0.5g is fitted in measurement sample pipe, with 200 DEG C of drying under reduced pressure 2 hours, the adsorbance of carbon dioxide is surveyed afterwards It is fixed.Temperature of the measurement is set to 25 DEG C, and carbon dioxide is imported in coupon, and the balance pressure obtained by constant volume method in coupon is reached The adsorbance of the carbon dioxide to 110KPa.Measurement result is shown in into table 3.
(measure of true specific gravity)
For each embodiment and each comparative example that are obtained as described above, surveyed by using the true specific gravity assay method of butanol True specific gravity is determined.Measurement result is shown in into table 3.
(measure of surface area)
The measure of surface area is carried out in the same manner as above.The value for calculating is shown in into table 1.
<The making of half-cell type lithium rechargeable battery>
The making of half-cell type lithium rechargeable battery is carried out in the same manner as above.
[first charge-discharge characteristic evaluation]
First charge-discharge characteristic evaluation is carried out in the same manner as above.As shown in following mathematical expressions (3), will just Secondary discharge capacity is multiplied by 100 and calculates first efficiency for charge-discharge divided by the value that primary charging capacity is obtained.In addition, by first charge and discharge The result of electrical characteristics evaluation is shown in table 1.
First efficiency for charge-discharge (%)=[initial discharge capacity (mAh/g)/primary charging capacity (mAh/g)] × 100 (3)
As shown in table 3, confirm any one embodiment and show that the phosphorus of the scope of regulation specified by the present invention contains Measure and less than the carbon dioxide adsorption of setting.In contrast, confirming the scope of phosphorus content in comparative example 4 less than regulation Lower limit, and the adsorbance of carbon dioxide is higher than significantly setting.Although in addition, it is regulation to confirm phosphorus content in comparative example 5 Scope, but carbon dioxide adsorption be setting more than.
In the battery behavior carried out using each embodiment is evaluated, high primary charging capacity and initial discharge is shown Capacity.The efficiency for charge-discharge gone out shown by each embodiment is significantly higher than each comparative example.Thus, the material with carbon element of embodiment shows The occlusion release of the chemical species such as lithium ion is excellent.
<The making of full cell type Li-ion secondary cell>
The making of full cell type Li-ion secondary cell is carried out in the same manner as above.
[low temperature environment test]
Low temperature environment test is carried out in the same manner as above.
With regard to above-mentioned low temperature environment discharge process, current value is drawn in transverse axis, after the longitudinal axis draws charge or discharge in 10 seconds Voltage, D.C. resistance (DC- when obtaining the charging in battery according to the absolute value of the slope of its near linear and during electric discharge IR), and according to the value low temperature environment characteristic is evaluated as described below.DC-IR is low to refer to that resistance is little, and output characteristics is good It is good.
D.C. resistance when D.C. resistance during charging is 195 below Ω and/or discharges is 215 below Ω ... ◎
D.C. resistance during charging more than 195 Ω and for 210 below Ω and discharge when D.C. resistance is more than 215 Ω and is 220 below Ω ... zero
D.C. resistance during charging is more than D.C. resistance when 210 Ω and/or electric discharge more than 220 Ω ... Δs
[composition of target compound]
The P conversion phosphorus contents and C conversion carbon contents on the surface of embodiment 12 are determined by XPS, their ratio of components is obtained P/C is simultaneously shown in table 4.
Also, the target compound on the surface of embodiment 12 is detected by XPS.By relative to detected institute By target compound constitute 100% each phosphorus compound and reduction phosphorus ratio of components be shown in table 4.
As shown in table 4, in confirming embodiment 12, triphenyl phosphine oxide ((C in target compound6H5)3P (=O)), triphenyl phasphine ((C6H5)3P) and each ratio of components of reduction phosphorus adds up to more than 50%, and reduce the ratio of components of phosphorus more than 0% and for 13% with Under.
[composition analysis of material with carbon element]
XPS：
For the material with carbon element precursor and embodiment 12 of embodiment 12, the element on surface is carried out quantitatively as described below. That is, carbon, oxygen, phosphorus, the content of nitrogen on the surface of material with carbon element precursor and embodiment 12 are determined by XPS, obtain each element relative to The ratio of components of their entirety.Show the result in table 5.
Composition analysis：
For the material with carbon element precursor and embodiment 12 of embodiment 12, the element in main body is determined as described below Amount.That is, by composition analysis as shown below to the carbon contained by the main body of material with carbon element precursor and embodiment 12, hydrogen, nitrogen, oxygen, The content of phosphorus is carried out quantitatively, has obtained ratio of components of each element relative to their entirety.Show the result in table 5.
Carbon, hydrogen and nitrogen are to use Atomic Absorption SpectrophotometerICP (Sumika Chemical Analysis Service, Ltd. systems Make, NCH-22F type Atomic Absorption SpectrophotometerICPs), carried out by Oxygen cycle burning, gas chromatography quantitative.Specifically, with about 850 DEG C make embodiment 12 burn completely, generate CO2Gas and H2O gases, and carbon and hydrogen are determined by gas chromatography Amount.Also, nitrogen is to be reduced after combustion and generated nitrogen (N2), carry out likewise by gas chromatography quantitative.
Oxygen is to use oxygen analyzer (HORIBA, Ltd., EMGA920 type oxygen analysis apparatus), by plus it is thermal melting, non- Dispersion infrared absorption carries out quantitative.Specifically, embodiment 12 is carried out under helium atmosphere, with about 2500 DEG C adding Heat, generates CO gases and CO2Gas, and carried out infrared detection.
Phosphorus be by ashing, acid dissolving, high-frequency induction coupled plasma optical emission spectra methods carry out it is quantitative.Specifically For, after embodiment 12 is ashed, in being dissolved in hydrochloric acid, filled by the spectrum analyses of high-frequency induction coupled plasma optical emission Put is carried out quantitatively to phosphorus.
No matter above-mentioned XPS and the result of composition analysis, confirm in embodiment 12 in the surface still carbon in main body More than 96%, carbon is main component to ratio of components.Results verification according to table 5 is arrived, with regard to oxygen and the ratio of components O/C of carbon, The ratio of components on the surface detected by XPS is big, and the ratio of the oxygen on the surface of embodiment 12 is higher than main body.In other words, embodiment 12 main body is compared with surface, and the ratio of carbon is higher.
As shown in table 5, embodiment 12 shows the ratio of components P of the phosphorus detected by X-ray photoelectron spectroscopic analysis (XPS) (XPS) more than the ratio of components P (COMP) of the phosphorus detected by composition analysis.Also, ratio of components P (COMP) is although be less than ratio of components P (XPS), but significant value is also showed that, phosphorus is not only significantly present in surface in embodiment 12, and is significantly present in main body In.
The surface area of the per unit volume of the material with carbon element of embodiment 12, embodiment 13 and embodiment 15 is 10000cm2/ cm3Above 16000cm2/cm3Scope above, shows good low-temperature characteristics.Wherein, the surface area of per unit volume is 12000cm2/cm3Embodiment 12 above, the material with carbon element of embodiment 13 show especially excellent low-temperature characteristics.
The mean square radius of gyration of the material with carbon element of embodiment 15 is contained in 1 μm24 μm of the above2In the range of, can prevent under hot environment Self discharge deterioration, and can expect to show the good coating to collector.
Embodiment 12 to the true specific gravity of the material with carbon element of embodiment 15 is 1.5g/cm3Above 1.7g/cm3Following scope. Thus, the value stabilization of the charge/discharge capacity of the secondary battery negative pole for being constituted using these, and can expect to contribute to secondary cell Life characteristic.
[High temperature storage characteristic evaluation]
Using embodiment make as described above, each and the full cell type Li-ion secondary cell of each comparative example, with Above-mentioned same mode has carried out the evaluation of High temperature storage characteristic.
The High temperature storage characteristic of each embodiment and each comparative example is shown in into table 3.
[life characteristics at high temperature evaluation]
Life characteristics at high temperature evaluation is carried out in the same manner as above.
The life characteristics at high temperature of each embodiment and each comparative example is shown in table 3.
[the decomposition evaluation of the lithium rechargeable battery after experiment of high-temperature load]
The decomposition of the lithium rechargeable battery after experiment of high-temperature load is evaluated and carried out in the same manner as above.
In each embodiment and each comparative example, lithium precipitation will be confirmed in 5 lithium rechargeable batteries in negative terminal surface The number of lithium rechargeable battery be shown in table 3.
According to the High temperature storage characteristic evaluation using each embodiment and the lithium rechargeable battery of each comparative example, show More than 80% high High temperature storage characteristic.The High temperature storage characteristic of especially embodiment is more than 85%, even if on 60 DEG C of left sides In the case of taking care of at a high temperature of the right side, also show that ratio that can be very high maintains the discharge capacity before keeping.According to the knot Even if fruit shows that the secondary battery negative pole material with carbon element of the invention contained by negative pole is in high temperature environments high charged state, Carbon structure can well be maintained.Speculate by maintaining the carbon structure, self discharge and negative terminal surface of the occlusion in the lithium of the material with carbon element The formation of overlay film become to be not likely to produce, therefore the secondary battery negative pole of the invention under hot environment can be maintained with high level Lithium occlusion release.
Also, according to the life characteristics at high temperature evaluation using each embodiment and the lithium rechargeable battery of each comparative example, Show more than 80% high High temperature storage characteristic.The life characteristics at high temperature of especially embodiment is more than 85%, even if At a high temperature of 55 DEG C or so in the case of Reusability, also show that ratio that can be very high maintains discharge capacity.Thus table The negative pole of the bright secondary battery negative pole material with carbon element containing present invention cycle characteristics in high temperature environments is excellent.
Also, the lithium rechargeable battery of each embodiment and each comparative example is decomposed after life characteristics at high temperature is evaluated, knot The lithium rechargeable battery of fruit embodiment is in the negative terminal surface precipitation to lithium unconfirmed.On the other hand, the lithium ion of comparative example Secondary cell confirms lithium and separates out with 20% ratio (specifically 5 in 1) in negative terminal surface.According to the result Even if showing secondary battery negative pole material with carbon element of the invention contained by negative pole in high temperature environments in the case of Reusability, The structure of carbon structure and negative plate can well be maintained.Speculate the structure by maintaining the carbon structure and negative plate, it is of the invention Its resistance variations can be mitigated with high level in the occlusion release of lithium of the negative pole in high temperature, as a result, the precipitation of lithium is pressed down System.
[table 4]
(* 1) does not separate the waveform of two kinds of phosphorus compounds, used as same blob detection.
[table 5]
Above-mentioned embodiment includes following technological thought.
(1) a kind of secondary battery negative pole resin combination, it contains：
Hydroxyl equivalent is the resin containing phenolic hydroxyl group of below 300g/eq；With
Boiling temperature or heat decomposition temperature exceed the phosphate ester or phosphorus that self condense temperature of the above-mentioned resin containing phenolic hydroxyl group Acid derivative.
(2) the secondary battery negative pole resin combination according to above-mentioned (1), wherein, relative to above-mentioned hydroxyl containing phenol The mass parts of resin 100 of base, contain above-mentioned phosphate ester or above-mentioned phosphoric acid are derivative with the scope below more than 3 mass parts 15 mass parts Thing.
(3) the secondary battery negative pole resin combination according to above-mentioned (1) or (2), wherein, above-mentioned phosphate ester or on The fusing point for stating phosphoric acid derivatives self condenses temperature less than above-mentioned the above-mentioned of the resin containing phenolic hydroxyl group.
(4) the secondary battery negative pole resin combination according to above-mentioned (3), wherein, above-mentioned phosphate ester or above-mentioned phosphorus The fusing point of the fusing point of acid derivative and the above-mentioned resin containing phenolic hydroxyl group exceedes room temperature and for less than 250 DEG C.
(5) the secondary battery negative pole resin combination according to above-mentioned (4), wherein, above-mentioned phosphate ester or above-mentioned phosphorus Melting end temp of the melting started temperature of acid derivative less than the above-mentioned resin containing phenolic hydroxyl group.
(6) the secondary battery negative pole resin combination according to any one of above-mentioned (1) is to (5), also containing solidification Agent,
The above-mentioned resin containing phenolic hydroxyl group is novolak phenolics.
(7) the secondary battery negative pole resin combination according to any one of above-mentioned (1) is to (6), wherein, above-mentioned phosphorus Acid esters is phosphotriester.
(8) the secondary battery negative pole resin combination according to above-mentioned (7), wherein, above-mentioned phosphotriester is phosphoric acid Triphenylmethyl methacrylate or above-mentioned triphenyl phosphate derivant.
(9) the secondary battery negative pole resin combination according to above-mentioned (8), wherein, above-mentioned triphenyl phosphate derives Thing is the compound represented by following chemical formula (1).
[(CH3)2C6H3O]2P(O)OC6II4OP(O)[OC6H3(CH3)2]2 (1)
(10) a kind of manufacture method of secondary battery negative pole material with carbon element, it is to use any one of above-mentioned (1) to (9) institute The manufacture method of the secondary battery negative pole material with carbon element of the secondary battery negative pole resin combination stated, above-mentioned secondary battery negative pole It is characterised by having with the manufacture method of material with carbon element：
First firing process, firing condition of maximum temperature during burning till less than 1000 DEG C is to above-mentioned secondary battery negative pole Burnt till with resin combination and generated material with carbon element precursor；With
Second firing process, maximum temperature during burning till is the firing condition of more than 1000 DEG C of temperature to above-mentioned first Above-mentioned material with carbon element precursor generated in firing process is burnt till, and thus generates material with carbon element.
(11) manufacture method of the secondary battery negative pole material with carbon element according to above-mentioned (10), wherein,
Above-mentioned first firing process is included：
In the melting stage, make the above-mentioned resin containing phenolic hydroxyl group contained by above-mentioned secondary battery negative pole resin combination and upper State phosphate ester or above-mentioned phosphoric acid derivatives melt；With
Material with carbon element precursor generation phase, forms the crystallite containing defat and/or the carbon of class graphene-structured.
(12) a kind of secondary battery negative pole material with carbon element, it is to use above-mentioned (1) to the secondary electricity any one of (9) Secondary battery negative pole material with carbon element manufactured by the negative pole resin combination of pond, the feature of above-mentioned secondary battery negative pole material with carbon element It is,
Containing carbon granule, the surface area of the per unit volume obtained according to the particle diameter distribution of number benchmark of above-mentioned carbon granule For 10000cm-1Above 16000cm-1Following scope.
(13) the secondary battery negative pole material with carbon element according to above-mentioned (12), wherein, above-mentioned carbon granule according to above-mentioned The mean square radius of gyration that particle diameter distribution is obtained is 1 μm24 μm of the above2Following scope.
(14) the secondary battery negative pole material with carbon element according to above-mentioned (12) or (13), wherein, above-mentioned carbon granule it is true Proportion is 1.5g/cm3Above 1.7g/cm3Following scope.
(15) the secondary battery negative pole material with carbon element according to any one of above-mentioned (12) are to (14), wherein, above-mentioned carbon Granule contains hard carbon, (002) face that above-mentioned hard carbon is obtained by using CuK alpha rays as radiogenic X-ray diffraction method it is flat Face interval d002For more than 0.340nm.
(16) the secondary battery negative pole material with carbon element according to above-mentioned (15), wherein, above-mentioned carbon granule contains 90 matter The above-mentioned hard carbon of amount more than %.
(17) the secondary battery negative pole material with carbon element according to above-mentioned (15) or (16), wherein, above-mentioned carbon granule contains Above-mentioned hard carbon and graphite.
(18) the secondary battery negative pole material with carbon element according to any one of above-mentioned (12) are to (17), it is used for secondary electricity Pond negative pole, and the High temperature storage characteristic shown in following High temperature storage characteristic evaluations is more than 85%,
Above-mentioned High temperature storage characteristic evaluation uses lithium rechargeable battery, above-mentioned lithium rechargeable battery to possess：
Secondary battery negative pole containing above-mentioned secondary battery negative pole material with carbon element；
Positive pole；
Electrolyte solution containing dissolving；With
Barrier film,
Above-mentioned High temperature storage characteristic evaluation uses above-mentioned lithium rechargeable battery, enters the charge and discharge cycles for being about to specify and implements The burin-in process of 5 circulations, and the 5th of above-mentioned charge and discharge cycles is circulated electric discharge when discharge capacity be measured and Discharge capacity I is set to,
Above-mentioned lithium rechargeable battery after using above-mentioned burin-in process, is set to 25mA/g and carries out constant current to fill by electric current density Electricity, from the moment that current potential reaches 4.2V, further keeps 4.2V and carries out constant-voltage charge, charges to electric current density and reaches Till 2.5mA/g, preparation is adjusted to the lithium rechargeable battery of charged state (State of Charge) 100%,
The above-mentioned lithium rechargeable battery of above-mentioned charged state 100% is taken care of in temperature is adjusted to 60 DEG C of drying machine 1 week,
After above-mentioned keeping, using above-mentioned lithium rechargeable battery, charged and discharged with the current value of 0.2C, with this As 1 circulation, implement the discharge and recharges of total 3 circulations, discharge capacity when determining the electric discharge of the 3rd circulation and be set to electric discharge Capacity II,
High temperature storage characteristic is calculated according to following mathematical expressions (4)：
High temperature storage characteristic (%)=[discharge capacity II (mAh/g)/discharge capacity I (mAh/g)] × 100 (4).
(19) the secondary battery negative pole material with carbon element according to any one of above-mentioned (12) are to (18), it is used for secondary electricity Pond negative pole, and the life characteristics at high temperature shown in following life characteristics at high temperature evaluations is more than 85%,
Above-mentioned life characteristics at high temperature evaluation uses lithium rechargeable battery, above-mentioned lithium rechargeable battery to possess：
Secondary battery negative pole containing above-mentioned secondary battery negative pole material with carbon element；
Positive pole；
Electrolyte solution containing dissolving；With
Barrier film,
Above-mentioned life characteristics at high temperature evaluation uses above-mentioned lithium rechargeable battery, enters the charge and discharge cycles for being about to specify and implements The burin-in process of 5 circulations,
Above-mentioned lithium rechargeable battery after using above-mentioned burin-in process, implements following charge and discharge cycles, in this, as 1 Circulation：With the constant-current charge of 1C to 4.2V under 55 DEG C of temperature environment, afterwards, decayed with the constant-voltage charge of 4.2V to current value After for 0.02C, kept for 30 minutes under 55 DEG C of temperature environment, then, with the constant-current discharge of 1C to 2.5V, and determine electric discharge Capacity and be set to discharge capacity III, afterwards, under 55 DEG C of temperature environment keep 30 minutes,
Then, further above-mentioned charge and discharge cycles are implemented into 99 to circulate, and the discharge and recharges for implementing total 100 circulations are followed Ring, and determine the 100th circulation electric discharge when discharge capacity and be set to discharge capacity IV,
Life characteristics at high temperature is calculated according to following mathematical expressions (5)：
Life characteristics at high temperature (%)=[discharge capacity IV (mAh/g)/discharge capacity III (mAh/g)] × 100 (5).
(20) a kind of secondary battery negative pole active substance, it is characterised in that containing any one of above-mentioned (12) to (19) Described secondary battery negative pole material with carbon element.
(21) a kind of secondary battery negative pole, it is characterised in that have：Use containing the secondary battery negative pole described in above-mentioned (20) The secondary battery negative pole active material layer of active substance；With the negative pole for being laminated with above-mentioned secondary battery negative pole active material layer Use collector.
(22) a kind of secondary cell, it is characterised in that possess secondary battery negative pole, the electrolyte and two described in above-mentioned (21) Primary cell positive pole.
(23) a kind of secondary battery negative pole resin containing phenolic hydroxyl group that is modified, it is characterised in that hydroxyl equivalent is 115g/ More than eq.
(24) resin containing phenolic hydroxyl group that is modified of the secondary battery negative pole according to above-mentioned (23), it contains following logical Structure represented by formula (4),
(wherein, in formula (4), P represents the structure containing phenolic hydroxyl group, and A and B represents that composition is modified containing phenolic hydroxyl group Resin main chain arbitrary atom or atom group, X represents any aryl, and n is more than 1 integer).
(25) resin containing phenolic hydroxyl group that is modified of the secondary battery negative pole according to above-mentioned (24), wherein, it is above-mentioned logical Formula (4) is following formulas (5),
(wherein, in formula (5), X1 to X4 separately represents the substituent group or hydrogen atom that benzene nucleus possesses).
(26) resin containing phenolic hydroxyl group that is modified of the secondary battery negative pole according to above-mentioned (25), wherein, it is above-mentioned logical More than any one in the above-mentioned X1 in formula (5) to above-mentioned X4 it is methyl.
(27) resin containing phenolic hydroxyl group that is modified of the secondary battery negative pole according to above-mentioned (26), wherein, it is above-mentioned logical Above-mentioned X1 and above-mentioned X2 in formula (5) is methyl, and two above-mentioned methyl are located at meta across 1 carbon atom.
(28) tree that the secondary battery negative pole according to any one of above-mentioned (23) are to (27) contains phenolic hydroxyl group with being modified Fat, wherein, above-mentioned secondary battery negative pole is phenol aralkyl resin with the modified resin containing phenolic hydroxyl group.
(29) tree that the secondary battery negative pole according to any one of above-mentioned (23) are to (28) contains phenolic hydroxyl group with being modified Fat, wherein, above-mentioned secondary battery negative pole is to make phenols with dimethylbenzene or dimethylbenzene modifiedization with the modified resin containing phenolic hydroxyl group The dimethylbenzene phenol-formaldehyde resin modified that compound is reacted and formed.
(30) a kind of secondary battery negative pole material with carbon element, it is characterised in that using any one of above-mentioned (23) to (29) institute The secondary battery negative pole stated is generated with the modified resin containing phenolic hydroxyl group.
(31) the secondary battery negative pole material with carbon element according to above-mentioned (30), it contains carbon granule, above-mentioned carbon granule The surface area of the per unit volume obtained according to the particle diameter distribution of number benchmark is 10000cm-1Above 16000cm-1Following model Enclose.
(32) the secondary battery negative pole material with carbon element according to above-mentioned (31), wherein, above-mentioned carbon granule contains hard carbon, on State the centre plane interval d in (002) face that hard carbon is obtained by using CuK alpha rays as radiogenic X-ray diffraction method002For More than 0.340nm.
(33) the secondary battery negative pole material with carbon element according to above-mentioned (32), wherein, above-mentioned carbon granule contains 90 matter The above-mentioned hard carbon of amount more than %.
(34) the secondary battery negative pole material with carbon element according to above-mentioned (32) or (33), wherein, above-mentioned carbon granule contains Above-mentioned hard carbon and graphite.
(35) a kind of secondary battery negative pole active substance, it is characterised in that containing any one of above-mentioned (30) to (34) institute The secondary battery negative pole material with carbon element stated.
(36) a kind of secondary battery negative pole, it is characterised in that have：Live containing the secondary battery negative pole described in above-mentioned (35) The negative electrode active material layer of property material；With the negative electrode collector for being laminated with above-mentioned negative electrode active material layer.
(37) a kind of secondary cell, it is characterised in that possess secondary battery negative pole, the electrolyte and two described in above-mentioned (36) Primary cell positive pole.
(38) a kind of secondary battery negative pole material with carbon element, it is characterised in that
Using carbon as main component,
Phosphorus is contained with the scope below more than 0.3 mass % 1.5 mass %, also,
The adsorbance of carbon dioxide is less than per unit weight 10ml/g.
(39) the secondary battery negative pole material with carbon element according to above-mentioned (38), wherein, the adsorbance of above-mentioned carbon dioxide For below per unit weight 5ml/g.
(40) the secondary battery negative pole material with carbon element according to above-mentioned (38) or (39), wherein, above-mentioned carbon dioxide Adsorbance is more than per unit weight 0.05ml/g.
(41) the secondary battery negative pole material with carbon element according to any one of above-mentioned (38) are to (40), with by X-ray light Phosphorus that electron spectroscopy analysis (XPS) are detected or the compound containing phosphorus as target compound,
Relative to the composition 100% of above-mentioned target compound, the triphenyl phosphine oxide, triphenyl phasphine and quilt contained by above-mentioned target compound The total amount of each ratio of components of the phosphorus after reduction is more than 50%, and it is above-mentioned be reduced after the ratio of components of phosphorus more than 0% and be Less than 13%.
(42) the secondary battery negative pole material with carbon element according to any one of above-mentioned (38) are to (41), wherein, by X-ray The oxygen that XPS Analysis (XPS) are detected is more than the group of the oxygen and carbon detected by composition analysis with the ratio of components O/C of carbon Into than O/C.
(43) the secondary battery negative pole material with carbon element according to any one of above-mentioned (38) are to (42), wherein, by X-ray Ratio of components Ps of the ratio of components P (XPS) of the phosphorus that XPS Analysis (XPS) are detected more than the phosphorus detected by composition analysis (COMP)。
(44) the secondary battery negative pole material with carbon element according to above-mentioned (43), wherein, above-mentioned P (COMP) is more than 0.
(45) the secondary battery negative pole material with carbon element according to any one of above-mentioned (38) are to (44), it contains carbon Grain, the surface area of the per unit volume obtained according to the particle diameter distribution of number benchmark of above-mentioned carbon granule is 10000cm-1More than 16000cm-1Following scope.
(46) the secondary battery negative pole material with carbon element according to above-mentioned (45), wherein, above-mentioned carbon granule according to above-mentioned The mean square radius of gyration that particle diameter distribution is obtained is 1 μm24 μm of the above2Following scope.
(47) the secondary battery negative pole material with carbon element according to above-mentioned (45) or (46), wherein, above-mentioned carbon granule it is true Proportion is 1.5g/cm3Above 1.7g/cm3Following scope.
(48) the secondary battery negative pole material with carbon element according to any one of above-mentioned (45) are to (47), wherein, above-mentioned carbon Granule contains hard carbon, (002) face that above-mentioned hard carbon is obtained by using CuK alpha rays as radiogenic X-ray diffraction method it is flat Face interval d002For more than 0.340nm.
(49) the secondary battery negative pole material with carbon element according to above-mentioned (48), wherein, above-mentioned carbon granule contains 90 matter The above-mentioned hard carbon of amount more than %.
(50) the secondary battery negative pole material with carbon element according to above-mentioned (48) or (49), wherein, above-mentioned carbon granule contains Above-mentioned hard carbon and graphite.
(51) the secondary battery negative pole material with carbon element according to any one of above-mentioned (38) are to (50), it is used for secondary electricity Pond negative pole, and the High temperature storage characteristic shown in following High temperature storage characteristic evaluations is more than 85%,
Above-mentioned High temperature storage characteristic evaluation uses lithium rechargeable battery, above-mentioned lithium rechargeable battery to possess：
Secondary battery negative pole containing above-mentioned secondary battery negative pole material with carbon element；
Positive pole；
Electrolyte solution containing dissolving；With
Barrier film,
Above-mentioned High temperature storage characteristic evaluation is entered the charge and discharge cycles for being about to specify using above-mentioned lithium rechargeable battery and implements 5 The burin-in process of individual circulation, and the 5th of above-mentioned charge and discharge cycles is circulated electric discharge when discharge capacity be measured and Discharge capacity I is set to,
Above-mentioned lithium rechargeable battery after using above-mentioned burin-in process, is set to 25mA/g and carries out constant current to fill by electric current density Electricity, from the moment that current potential reaches 4.2V, further keeps 4.2V and carries out constant-voltage charge, charges to electric current density and reaches Till 2.5mA/g, preparation is adjusted to the lithium rechargeable battery of charged state (State of Charge) 100%,
The above-mentioned lithium rechargeable battery of above-mentioned charged state 100% is taken care of in temperature is adjusted to 60 DEG C of drying machine 1 week,
After above-mentioned keeping, using above-mentioned lithium rechargeable battery, charged and discharged with the current value of 0.2C, with this As 1 circulation, implement the discharge and recharges of total 3 circulations, discharge capacity when determining the electric discharge of the 3rd circulation and be set to electric discharge Capacity II,
High temperature storage characteristic is calculated according to following mathematical expressions (4).
High temperature storage characteristic (%)=[discharge capacity II (mAh/g)/discharge capacity I (mAh/g)] × 100 (4)
(52) the secondary battery negative pole material with carbon element according to any one of above-mentioned (38) are to (51), it is used for secondary electricity Pond negative pole, and the life characteristics at high temperature shown in following life characteristics at high temperature evaluations is more than 85%,
Above-mentioned life characteristics at high temperature evaluation uses lithium rechargeable battery, above-mentioned lithium rechargeable battery to possess：
Secondary battery negative pole containing above-mentioned secondary battery negative pole material with carbon element；
Positive pole；
Electrolyte solution containing dissolving；With
Barrier film,
Above-mentioned life characteristics at high temperature evaluation uses above-mentioned lithium rechargeable battery, enters the charge and discharge cycles for being about to specify and implements The burin-in process of 5 circulations,
Above-mentioned lithium rechargeable battery after using above-mentioned burin-in process, implements following charge and discharge cycles, in this, as 1 Individual circulation：With the constant-current charge of 1C to 4.2V under 55 DEG C of temperature environment, afterwards, declined to current value with the constant-voltage charge of 4.2V After being kept to 0.02C, keep under 55 DEG C of temperature environment 30 minutes, then, with the constant-current discharge of 1C to 2.5V, and measure is put Capacitance and be set to discharge capacity III, afterwards, under 55 DEG C of temperature environment keep 30 minutes,
Then, further above-mentioned charge and discharge cycles are implemented into 99 to circulate, and the discharge and recharges for implementing total 100 circulations are followed Ring, and determine the 100th circulation electric discharge when discharge capacity and be set to discharge capacity IV,
Life characteristics at high temperature is calculated according to following mathematical expressions (5)：
Life characteristics at high temperature (%)=[discharge capacity IV (mAh/g)/discharge capacity III (mAh/g)] × 100 (5).
(53) a kind of secondary battery negative pole active substance, it is characterised in that containing any one of above-mentioned (38) to (52) Described secondary battery negative pole material with carbon element.
(54) a kind of secondary battery negative pole, it is characterised in that have：Use containing the secondary battery negative pole described in above-mentioned (53) The secondary battery negative pole active material layer of active substance；With the negative pole for being laminated with above-mentioned secondary battery negative pole active material layer Use collector.
(55) a kind of secondary cell, it is characterised in that possess secondary battery negative pole, the electrolyte and two described in above-mentioned (54) Primary cell positive pole.
Symbol description
10- negative poles, 12- negative electrode active material layers, 14- negative electrode collectors, 20- positive poles, 22- positive electrode active material layers, 24- Positive electrode collector, 30- barrier films, 40- electrolyte, 100- lithium rechargeable batteries.

Claims (55)

1. a kind of secondary battery negative pole material with carbon element, it is characterised in that：
Using carbon as main component,
Phosphorus is contained with the scope below more than 0.3 mass % 1.5 mass %, also,
The adsorbance of carbon dioxide is less than per unit weight 10ml/g.
2. secondary battery negative pole material with carbon element according to claim 1, it is characterised in that：
The adsorbance of the carbon dioxide is below per unit weight 5ml/g.
3. secondary battery negative pole material with carbon element according to claim 1 and 2, it is characterised in that：
The adsorbance of the carbon dioxide is more than per unit weight 0.05ml/g.
4. secondary battery negative pole material with carbon element according to any one of claim 1 to 3, it is characterised in that：
Compound using the phosphorus detected by X-ray photoelectron spectroscopic analysis (XPS) or containing phosphorus as target compound,
Relative to the composition 100% of the target compound, triphenyl phosphine oxide, triphenyl phasphine contained by the target compound and it is reduced The total amount of each ratio of components of phosphorus afterwards be more than 50%, and it is described be reduced after phosphorus ratio of components be less than 13%.
5. secondary battery negative pole material with carbon element according to any one of claim 1 to 4, it is characterised in that：
The oxygen detected by X-ray photoelectron spectroscopic analysis (XPS) is more than what is detected by composition analysis with the ratio of components O/C of carbon The ratio of components O/C of oxygen and carbon.
6. secondary battery negative pole material with carbon element according to any one of claim 1 to 5, it is characterised in that：
The ratio of components P of the phosphorus detected by X-ray photoelectron spectroscopic analysis (XPS)(XPS)More than the phosphorus detected by composition analysis Ratio of components P(COMP)。
7. secondary battery negative pole material with carbon element according to claim 6, it is characterised in that：
The P(COMP)More than 0.
8. secondary battery negative pole material with carbon element according to any one of claim 1 to 7, it is characterised in that：
Containing carbon granule, the surface area of the per unit volume obtained according to the particle diameter distribution of number benchmark of the carbon granule is 10000cm-1Above 16000cm-1Following scope.
9. secondary battery negative pole material with carbon element according to claim 8, it is characterised in that：
The carbon granule is 1 μm according to the mean square radius of gyration that the particle diameter distribution is obtained24 μm of the above2Following scope.
10. secondary battery negative pole material with carbon element according to claim 8 or claim 9, it is characterised in that：
The true specific gravity of the carbon granule is 1.5g/cm3Above 1.7g/cm3Following scope.
The 11. secondary battery negative pole material with carbon elements according to any one of claim 8 to 10, it is characterised in that：
The carbon granule contains hard carbon, and the hard carbon is obtained by using CuK alpha rays as radiogenic X-ray diffraction method (002) the centre plane interval d in face002For more than 0.340nm.
12. secondary battery negative pole material with carbon elements according to claim 11, it is characterised in that：
The carbon granule contains the hard carbons more than 90 mass %.
The 13. secondary battery negative pole material with carbon elements according to claim 11 or 12, it is characterised in that：
The carbon granule contains the hard carbon and graphite.
The 14. secondary battery negative pole material with carbon elements according to any one of claim 1 to 13, it is characterised in that：
The secondary battery negative pole is used for secondary battery negative pole with material with carbon element, and shows in following High temperature storage characteristic evaluations High temperature storage characteristic be more than 85%,
The High temperature storage characteristic evaluation uses lithium rechargeable battery, the lithium rechargeable battery to possess：
Secondary battery negative pole containing the secondary battery negative pole material with carbon element；
Positive pole；
Electrolyte solution containing dissolving；With
Barrier film,
The High temperature storage characteristic evaluation is entered the charge and discharge cycles enforcement 5 for being about to specify using the lithium rechargeable battery and is followed The burin-in process of ring, and the 5th of the charge and discharge cycles is circulated electric discharge when discharge capacity be measured and be set to Discharge capacity I,
The lithium rechargeable battery after using the burin-in process, electric current density is set to into 25mA/g carries out constant-current charge, From the moment that current potential reaches 4.2V, further keep 4.2V and carry out constant-voltage charge, charge to electric current density and reach 2.5mA/g Till, preparation is adjusted to the lithium rechargeable battery of charged state (State of Charge) 100%,
The lithium rechargeable battery of the charged state 100% is taken care of 1 week in temperature is adjusted to 60 DEG C of drying machine,
After the keeping, using the lithium rechargeable battery, charged and discharged with the current value of 0.2C, in this, as 1 circulation, implements the discharge and recharges of total 3 circulations, discharge capacity when determining the electric discharge of the 3rd circulation and be set to discharge capacity II,
High temperature storage characteristic is calculated according to following mathematical expressions (4)：
High temperature storage characteristic (%)=[discharge capacity II (mAh/g)/discharge capacity I (mAh/g)] × 100 (4).
The 15. secondary battery negative pole material with carbon elements according to any one of claim 1 to 14, it is characterised in that：
The secondary battery negative pole is used for secondary battery negative pole with material with carbon element, and shows in following life characteristics at high temperature evaluations Life characteristics at high temperature be more than 85%,
The life characteristics at high temperature evaluation uses lithium rechargeable battery, the lithium rechargeable battery to possess：
Secondary battery negative pole containing the secondary battery negative pole material with carbon element；
Positive pole；
Electrolyte solution containing dissolving；With
Barrier film,
The life characteristics at high temperature evaluation uses the lithium rechargeable battery, enters the charge and discharge cycles for being about to specify and implements 5 The burin-in process of circulation,
The lithium rechargeable battery after using the burin-in process, implements following charge and discharge cycles, follows in this, as 1 Ring：With the constant-current charge of 1C to 4.2V under 55 DEG C of temperature environment, afterwards, decayed to current value with the constant-voltage charge of 4.2V After 0.02C, keep under 55 DEG C of temperature environment 30 minutes, then, with the constant-current discharge of 1C to 2.5V, and determine electric discharge appearance Measure and be set to discharge capacity III, afterwards, kept for 30 minutes under 55 DEG C of temperature environment,
Then, further the charge and discharge cycles are implemented into 99 to circulate, and implement the charge and discharge cycles of total 100 circulations, And determine the 100th circulation electric discharge when discharge capacity and be set to discharge capacity IV,
Life characteristics at high temperature is calculated according to following mathematical expressions (5)：
Life characteristics at high temperature (%)=[discharge capacity IV (mAh/g)/discharge capacity III (mAh/g)] × 100 (5).
A kind of 16. secondary battery negative pole active substances, it is characterised in that：
Containing the secondary battery negative pole material with carbon element any one of claim 1 to 15.
17. a kind of secondary battery negative poles, it is characterised in that have：
Secondary battery negative pole active material layer containing the secondary battery negative pole active substance described in claim 16；And layer It is laminated with the negative pole collector of the secondary battery negative pole active material layer.
A kind of 18. secondary cells, it is characterised in that：
Possess secondary battery negative pole described in claim 17, electrolyte and anode of secondary battery.
19. a kind of secondary battery negative pole resin combinations, it is characterised in that contain：
Hydroxyl equivalent is the resin containing phenolic hydroxyl group of below 300g/eq；With
Boiling temperature or heat decomposition temperature exceed the phosphate ester or phosphoric acid that self condense temperature of the resin containing phenolic hydroxyl group and spread out It is biological.
20. secondary battery negative pole resin combinations according to claim 19, it is characterised in that：
Relative to the mass parts of resin 100 containing phenolic hydroxyl group, with the scope below more than 3 mass parts 15 mass parts containing State phosphate ester or the phosphoric acid derivatives.
The 21. secondary battery negative pole resin combinations according to claim 19 or 20, it is characterised in that：
The fusing point of the phosphate ester or the phosphoric acid derivatives is less than described in the resin containing phenolic hydroxyl group and self condenses temperature.
22. secondary battery negative pole resin combinations according to claim 21, it is characterised in that：
The fusing point of the fusing point and the resin containing phenolic hydroxyl group of the phosphate ester or the phosphoric acid derivatives exceed room temperature and For less than 250 DEG C.
23. secondary battery negative pole resin combinations according to claim 22, it is characterised in that：
The melting started temperature of the phosphate ester or the phosphoric acid derivatives is tied less than the melting of the resin containing phenolic hydroxyl group Shu Wendu.
The 24. secondary battery negative pole resin combinations according to any one of claim 19 to 23, it is characterised in that：
Also contain firming agent,
The resin containing phenolic hydroxyl group is novolak phenolics.
The 25. secondary battery negative pole resin combinations according to any one of claim 19 to 24, it is characterised in that：
The phosphate ester is phosphotriester.
26. secondary battery negative pole resin combinations according to claim 25, it is characterised in that：
The phosphotriester is triphenyl phosphate or the triphenyl phosphate derivant.
27. secondary battery negative pole resin combinations according to claim 26, it is characterised in that：
The triphenyl phosphate derivant is the compound represented by following chemical formula (1)：
[(CH3)2C6H3O]2P(O)OC6H1OP(O)[OC6H3(CH3)2]2 (1)。
A kind of 28. manufacture methods of secondary battery negative pole material with carbon element, it is that usage right is required any one of 19 to 27 Secondary battery negative pole resin combination secondary battery negative pole material with carbon element manufacture method, the secondary battery negative pole uses The manufacture method of material with carbon element is characterised by having：
First firing process, firing condition of maximum temperature during burning till less than 1000 DEG C is to the secondary battery negative pole tree Oil/fat composition is burnt till and is generated material with carbon element precursor；With
Second firing process, maximum temperature during burning till is that the firing condition of more than 1000 DEG C of temperature burns till to described first The material with carbon element precursor generated in operation is burnt till, and thus generates material with carbon element.
The manufacture method of 29. secondary battery negative pole material with carbon elements according to claim 28, it is characterised in that：
First firing process is included：
In the melting stage, make the resin containing phenolic hydroxyl group and the phosphorus described in contained by the secondary battery negative pole resin combination Acid esters or the phosphoric acid derivatives melt；With
Material with carbon element precursor generation phase, forms the crystallite containing defat and/or the carbon of class graphene-structured.
A kind of 30. secondary battery negative pole material with carbon elements, it is the secondary cell any one of usage right requirement 19 to 27 The secondary battery negative pole material with carbon element that negative pole is manufactured with resin combination, the feature of the secondary battery negative pole material with carbon element exists In：
Containing carbon granule, the surface area of the per unit volume obtained according to the particle diameter distribution of number benchmark of the carbon granule is 10000cm-1Above 16000cm-1Following scope.
31. secondary battery negative pole material with carbon elements according to claim 30, it is characterised in that：
The carbon granule is 1 μm according to the mean square radius of gyration that the particle diameter distribution is obtained24 μm of the above2Following scope.
The 32. secondary battery negative pole material with carbon elements according to claim 30 or 31, it is characterised in that：
The true specific gravity of the carbon granule is 1.5g/cm3Above 1.7g/cm3Following scope.
The 33. secondary battery negative pole material with carbon elements according to any one of claim 30 to 32, it is characterised in that：
The carbon granule contains hard carbon, and the hard carbon is obtained by using CuK alpha rays as radiogenic X-ray diffraction method (002) the centre plane interval d in face002For more than 0.340nm.
34. secondary battery negative pole material with carbon elements according to claim 33, it is characterised in that：
The carbon granule contains the hard carbons more than 90 mass %.
The 35. secondary battery negative pole material with carbon elements according to claim 33 or 34, it is characterised in that：
The carbon granule contains the hard carbon and graphite.
The 36. secondary battery negative pole material with carbon elements according to any one of claim 30 to 35, it is characterised in that：
The secondary battery negative pole is used for secondary battery negative pole with material with carbon element, and shows in following High temperature storage characteristic evaluations High temperature storage characteristic be more than 85%,
The High temperature storage characteristic evaluation uses lithium rechargeable battery, the lithium rechargeable battery to possess：
Secondary battery negative pole containing the secondary battery negative pole material with carbon element；
Positive pole；
The electrolyte that electrolyte dissolution is formed；With
Barrier film,
The High temperature storage characteristic evaluation uses the lithium rechargeable battery, enters the charge and discharge cycles for being about to specify and implements 5 The burin-in process of circulation, and the 5th of the charge and discharge cycles is circulated electric discharge when discharge capacity be measured and set For discharge capacity I,
The lithium rechargeable battery after using the burin-in process, electric current density is set to into 25mA/g carries out constant-current charge, From the moment that current potential reaches 4.2V, further keep 4.2V and carry out constant-voltage charge, charge to electric current density and reach 2.5mA/g Till, preparation is adjusted to the lithium rechargeable battery of charged state (State of Charge) 100%,
The lithium rechargeable battery of the charged state 100% is taken care of 1 week in temperature is adjusted to 60 DEG C of drying machine,
After the keeping, using the lithium rechargeable battery, charged and discharged with the current value of 0.2C, in this, as 1 circulation, implements the discharge and recharges of total 3 circulations, discharge capacity when determining the electric discharge of the 3rd circulation and be set to discharge capacity II,
High temperature storage characteristic is calculated according to following mathematical expressions (4)：
High temperature storage characteristic (%)=[discharge capacity II (mAh/g)/discharge capacity I (mAh/g)] × 100 (4).
The 37. secondary battery negative pole material with carbon elements according to any one of claim 30 to 36, it is characterised in that：
The secondary battery negative pole is used for secondary battery negative pole with material with carbon element, and shows in following life characteristics at high temperature evaluations Life characteristics at high temperature be more than 85%,
The life characteristics at high temperature evaluation uses lithium rechargeable battery, the lithium rechargeable battery to possess：
Secondary battery negative pole containing the secondary battery negative pole material with carbon element；
Positive pole；
The electrolyte that electrolyte dissolution is formed；With
Barrier film,
The life characteristics at high temperature evaluation uses the lithium rechargeable battery, enters the charge and discharge cycles for being about to specify and implements 5 The burin-in process of circulation,
The lithium rechargeable battery after using the burin-in process, implements following charge and discharge cycles, follows in this, as 1 Ring：With the constant-current charge of 1C to 4.2V under 55 DEG C of temperature environment, afterwards, decayed to current value with the constant-voltage charge of 4.2V After 0.02C, keep under 55 DEG C of temperature environment 30 minutes, then, with the constant-current discharge of 1C to 2.5V, and determine electric discharge appearance Measure and be set to discharge capacity III, afterwards, kept for 30 minutes under 55 DEG C of temperature environment,
Then, further the charge and discharge cycles are implemented into 99 to circulate, and implement the charge and discharge cycles of total 100 circulations, And determine the 100th circulation electric discharge when discharge capacity and be set to discharge capacity IV,
Life characteristics at high temperature is calculated according to following mathematical expressions (5)：
Life characteristics at high temperature (%)=[discharge capacity IV (mAh/g)/discharge capacity III (mAh/g)] × 100 (5).
A kind of 38. secondary battery negative pole active substances, it is characterised in that：
Containing the secondary battery negative pole material with carbon element any one of claim 30 to 37.
39. a kind of secondary battery negative poles, it is characterised in that have：
Secondary battery negative pole active material layer containing the secondary battery negative pole active substance described in claim 38；With
It is laminated with the negative pole collector of the secondary battery negative pole active material layer.
A kind of 40. secondary cells, it is characterised in that：
Possess secondary battery negative pole described in claim 39, electrolyte and anode of secondary battery.
A kind of 41. secondary battery negative poles resins containing phenolic hydroxyl group that are modified, it is characterised in that：
Hydroxyl equivalent is more than 115g/eq.
The 42. secondary battery negative poles according to claim 41 resins containing phenolic hydroxyl group that are modified, it is characterised in that contain Structure represented by following formulas (4)：
Wherein, in formula (4), P represents the structure containing phenolic hydroxyl group, and A and B is represented and constituted the modified resin containing phenolic hydroxyl group Main chain arbitrary atom or atom group, X represents any aryl, and n is more than 1 integer.
The 43. secondary battery negative poles according to claim 42 resins containing phenolic hydroxyl group that are modified, it is characterised in that：
The formula (4) is following formulas (5)：
Wherein, in formula (5), X1 to X4 separately represents the substituent group or hydrogen atom that benzene nucleus possesses.
The 44. secondary battery negative poles according to claim 43 resins containing phenolic hydroxyl group that are modified, it is characterised in that：
More than any one in the X1 to the X4 in the formula (5) it is methyl.
The 45. secondary battery negative poles according to claim 44 resins containing phenolic hydroxyl group that are modified, it is characterised in that：
The X1 and the X2 in the formula (5) is methyl, and 2 methyl are located at meta across 1 carbon atom.
46. resins containing phenolic hydroxyl group that are modified of the secondary battery negative poles according to any one of claim 41 to 45, its It is characterised by：
The secondary battery negative pole is phenol aralkyl resin with the modified resin containing phenolic hydroxyl group.
47. resins containing phenolic hydroxyl group that are modified of the secondary battery negative poles according to any one of claim 41 to 46, its It is characterised by：
The secondary battery negative pole is to make phenols with dimethylbenzene or dimethylbenzene modified compound with the modified resin containing phenolic hydroxyl group The dimethylbenzene phenol-formaldehyde resin modified for being reacted and being formed.
A kind of 48. secondary battery negative pole material with carbon elements, it is characterised in that：
Usage right requires that the secondary battery negative pole any one of 41 to 47 is generated with the modified resin containing phenolic hydroxyl group.
49. secondary battery negative pole material with carbon elements according to claim 48, it is characterised in that：
Containing carbon granule, the surface area of the per unit volume obtained according to the particle diameter distribution of number benchmark of the carbon granule is 10000cm-1Above 16000cm-1Following scope.
50. secondary battery negative pole material with carbon elements according to claim 49, it is characterised in that：
The carbon granule contains hard carbon, and the hard carbon is obtained by using CuK alpha rays as radiogenic X-ray diffraction method (002) the centre plane interval d in face002For more than 0.340nm.
51. secondary battery negative pole material with carbon elements according to claim 50, it is characterised in that：
The carbon granule contains the hard carbons more than 90 mass %.
The 52. secondary battery negative pole material with carbon elements according to claim 50 or 51, it is characterised in that：
The carbon granule contains the hard carbon and graphite.
A kind of 53. secondary battery negative pole active substances, it is characterised in that：
Containing the secondary battery negative pole material with carbon element any one of claim 48 to 52.
54. a kind of secondary battery negative poles, it is characterised in that have：
Negative electrode active material layer containing the secondary battery negative pole active substance described in claim 53；With
It is laminated with the negative electrode collector of the negative electrode active material layer.
55. a kind of secondary cells, it is characterised in that possess：
Secondary battery negative pole described in claim 54；Electrolyte；And anode of secondary cell.
CN201580044501.2A 2014-08-29 2015-08-26 Secondary battery negative electrode resin composition, method for producing secondary battery negative electrode carbon material, secondary battery negative electrode carbon material, modified phenolic hydroxyl group for use in secondary battery negative electrode, secondary battery negative electrode active material, secondary battery negative electrode, and secondary battery Pending CN106575769A (en)

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JP2006089348A (en) * 2004-09-27 2006-04-06 Sumitomo Bakelite Co Ltd Method for producing carbon material, negative electrode material for secondary battery, and nonaqueous electrolyte secondary battery
JP2007042571A (en) * 2005-06-28 2007-02-15 Hitachi Chem Co Ltd Carbon particle for anode of lithium secondary battery, and carbon anode for lithium secondary battery and lithium secondary battery using the same

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EP0418514A1 (en) * 1989-07-29 1991-03-27 Sony Corporation Carbonaceous material and a non-aqueous electrochemical cell using the same
JPH10241690A (en) * 1997-02-27 1998-09-11 Toyota Central Res & Dev Lab Inc Lithium secondary battery negative electrode
JP2006089348A (en) * 2004-09-27 2006-04-06 Sumitomo Bakelite Co Ltd Method for producing carbon material, negative electrode material for secondary battery, and nonaqueous electrolyte secondary battery
JP2007042571A (en) * 2005-06-28 2007-02-15 Hitachi Chem Co Ltd Carbon particle for anode of lithium secondary battery, and carbon anode for lithium secondary battery and lithium secondary battery using the same

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