CN104904048A - Positive electrode active substance, positive electrode for nonaqueous electrolyte secondary cell, nonaqueous electrolyte secondary cell, and method for producing positive electrode active substance - Google Patents

Positive electrode active substance, positive electrode for nonaqueous electrolyte secondary cell, nonaqueous electrolyte secondary cell, and method for producing positive electrode active substance Download PDF

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CN104904048A
CN104904048A CN201480004291.XA CN201480004291A CN104904048A CN 104904048 A CN104904048 A CN 104904048A CN 201480004291 A CN201480004291 A CN 201480004291A CN 104904048 A CN104904048 A CN 104904048A
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active material
positive active
particle
lithium
source
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今井英
风间吉则
幡谷耕二
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Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
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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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • 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 Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention discloses a positive electrode active substance, a positive electrode for nonaqueous electrolyte secondary cell, a nonaqueous electrolyte secondary cell, and a method for producing positive electrode active substance. The positive electrode active substance (1) is characterized in that particles (5) containing iron or iron carbide are added to a manganese-doped lithium iron silicate (3) represented by general formula Li2Fe1-xMnxSiO4 (0.25 <= x < 1). The method for producing the positive electrode active substance is characterized by comprising the following: a step (a) for synthesizing precursor particles using a lithium source, an iron source, a manganese source, and a silicon source; a step (b) for mixing a carbon source in the precursor particles; and a step (c) for calcining the precursor particles mixed with the carbon source under an inert atmosphere. Preferably the positive electrode active substance is carbon-coated by annealing under a hydrocarbon gas atmosphere.

Description

The manufacture method of positive active material, positive electrode for nonaqueous electrolyte secondary battery, rechargeable nonaqueous electrolytic battery and positive active material
Technical field
The present invention relates to silicic acid ferrimanganic lithium system positive active material etc. used in rechargeable nonaqueous electrolytic battery.
Background technology
In recent years, along with mobile and the multifunction of electronic equipment, the secondary cell as driving power becomes one of most important parts.Particularly, lithium rechargeable battery is high because of the energy density obtained by the high voltage of positive active material used and negative electrode active material, therefore so that replace NiCd battery, Ni hydrogen battery in the past, occupies the position of the main flow of secondary cell.But, the cobalt acid lithium (LiCoO becoming standard used in present Li ion battery 2) be the Li ion secondary battery combined of the carbon-based negative electrode active material of positive active material and graphite body, the power consumption of nearest high function high capacity electronic unit cannot being provided fully, the performance as carrying required by power supply cannot being met.
And then because cobalt acid lithium employs the cobalt as rare metal, therefore the restriction of resource is large, and price is high, has problem in price rigidity.In addition, when cobalt acid lithium reaches the high temperature of more than 180 DEG C, a large amount of oxygen will be released, therefore when abnormal heating or the short circuit of battery time likely set off an explosion.
Thus, with cobalt acid lithium compared with excellent heat stability, with ferric metasilicate lithium (Li 2feSiO 4), manganese silicate of lithium (Li 2mnSiO 4) headed by the silicic acid transition metal lithium with olivine structural, as meet resource aspect, cost aspect, secure context material receive publicity.
Particularly manganese silicate of lithium is large with ferric metasilicate lithium phase specific capacity, and the silicic acid ferrimanganic lithium therefore containing manganese receives much concern.
But the surface of manganese silicate of lithium is difficult to the carbon carried out by organic carburizing reagent and is coated to, at the silicic acid ferrimanganic lithium (Li of the manganese containing more than 25mol% 2fe 1-xmn xsiO 4(0.25≤x < 1)) in, have and be difficult to utilize the annealing in process in the appropriate hydrocarbon gas atmosphere of short time to give the problem of enough conductivity.
Fig. 8 is used to be described this problem.Fig. 8 (a) ~ (d) is at Li 2fe 1-xmn xsiO 4be in positive active material, the ratio x of Mn shared in the total of Fe and Mn is set to 0,0.25,0.5,1.0 each positive active material, the figure of the passing of powder conductivity when representing the annealing in process time changed in butane atmosphere.Before butane treatment, the powder conductivity of any positive active material does not all have large difference, but after the butane treatment of 10 minutes, the Li only not containing Mn 2feSiO 4((a): x=0) demonstrates 1 × 10 -1the good powder conductivity of about S/cm.The positive active material ((c): x=0.50) of the positive active material ((b): x=0.25) for the Mn containing 25mol% and the Mn containing 50mol%, can obtain good powder conductivity by the butane treatment of carrying out 60 minutes.In addition, for the positive active material of the Mn containing 100mol%, i.e. Li 2mnSiO 4((d): x=1.0), in order to obtain good powder conductivity, need the butane treatment of carrying out 90 minutes, the ratio of known Mn is higher, longer for the butane treatment time obtaining good powder conductivity, is more difficult to carry out carbon and is coated to.
On the other hand, being coated to carry out carbon to manganese silicate of lithium, reporting that the surface of the particle by comprising manganese silicate of lithium utilized and being coated to containing the coating of ferric metasilicate lithium and the electrode active material (reference patent documentation 1) that obtain.
Prior art document
Patent documentation
Patent documentation 1: No. 2011-181375, Japanese Unexamined Patent Publication
Summary of the invention
Invent problem to be solved
Manganese silicate of lithium is compared with ferric metasilicate lithium, and the carbon being difficult to carry out fully surface is coated to, and therefore has the problem cannot bringing enough conductivity to the positive active material employing silicic acid ferrimanganic lithium.
In addition, in the electrode active material recorded in patent documentation 1, in order to solve the coating problem of carbon, the surface ferric metasilicate lithium of large manganese silicate of lithium particle is coated to.But, there are the structure of electrode active material or the problem of manufacture method complexity.
For the scheme of dealing with problems
The present invention completes in view of the above-mentioned problems, its object is to, and provides containing silicic acid ferrimanganic lithium and the annealing of the appropriate hydrocarbon gas of short time can be utilized to realize the coating positive active material of carbon.
The present inventor finds, when positive active material contains the particulate of iron or cementite, utilizes the annealing by appropriate hydrocarbon gas, can carry out carbon at short notice and be coated to, so that complete the present invention.
That is, the present invention possesses following feature.
(1) positive active material, is characterized in that, with general formula Li 2fe 1-xmn xsiO 4in the silicic acid ferrimanganic lithium that (0.25≤x < 1) represents, comprise the particle containing iron or cementite.
(2) there is the above-mentioned positive active material of following feature, wherein, replace a part of Fe and/or Mn, be replaced at least one party of Co or Ni.
(3) there is the above-mentioned positive active material of following feature, wherein, replace a part of Fe and/or Mn, be replaced into Mg, Ca, Ti, V, Cr, Cu, Zn, Sr, Zr, Mo at least any one.
(4) there is the above-mentioned positive active material of following feature, wherein, replace a part of Li, be replaced into Mg, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Zr, Mo at least any one.
(5) have the above-mentioned positive active material of following feature, wherein, there is the particle containing iron or cementite on the border between the particle of silicic acid ferrimanganic lithium.
(6) having the above-mentioned positive active material of following feature, wherein, is comprise the particle of described silicic acid ferrimanganic lithium and the described offspring containing the particle of iron or cementite.
(7) there is the above-mentioned positive active material of following feature, wherein, there is on the surface of described positive active material carbon and be coated to.
(8) have the above-mentioned positive active material of following feature, wherein, powder conductivity is 10 -3more than S/cm.
(9) have the above-mentioned positive active material of following feature, wherein, the content of the carbon in described positive active material is more than 1.5 % by weight.
(10) have the above-mentioned positive active material of following feature, wherein, the described average grain diameter containing the particle of iron or cementite is 100nm ~ 2 μm.
(11) positive electrode for nonaqueous electrolyte secondary battery, is characterized in that, has collector body and the positive electrode active material layer containing above-mentioned positive active material at least being simultaneously positioned at described collector body.
(12) a kind of rechargeable nonaqueous electrolytic battery, it is characterized in that, there is above-mentioned positive electrode for nonaqueous electrolyte secondary battery, the negative pole store and discharge lithium ion and the distance piece be configured between described positive pole and described negative pole can be inhaled, in the electrolyte with lithium-ion-conducting, described positive pole, described negative pole and described distance piece are set.
(13) one comprises with general formula Li 2fe 1-xmn xsiO 4the manufacture method of the positive active material of the silicic acid ferrimanganic lithium that (0.25≤x < 1) represents and the particle containing iron or cementite, it is characterized in that possessing: use lithium source, source of iron, manganese source and silicon source to synthesize the operation (a) of precursor particle; The operation (b) of mixed carbon source in described precursor particle; With the operation (c) that the described precursor particle be mixed with described carbon source is burnt till under an inert atmosphere.
(14) there is the manufacture method of the above-mentioned positive active material of following feature, wherein, after described operation (c), also possess the operation (d) of being annealed under appropriate hydrocarbon gas atmosphere by described positive active material.
(15) there is the manufacture method of the above-mentioned positive active material of following feature; wherein; in described operation (a); described lithium source, described source of iron, described manganese source and described silicon source are supplied in flame with combustion-supporting property gas with vaporific drop together with imflammable gas, synthesis particle mixture.
(16) there is the manufacture method of the above-mentioned positive active material of following feature, wherein, described carbon source be polyvinyl alcohol, PVP, carboxymethyl cellulose, acetylcellulose, sucrose, carbon black any one more than.
The effect of invention
According to the present invention, can provide containing silicic acid ferrimanganic lithium and the annealing of the appropriate hydrocarbon gas of short time can be utilized to realize the coating positive active material of carbon.
Accompanying drawing explanation
Fig. 1 is the summary section of the positive active material 1 represented involved by present embodiment.
Fig. 2 is that the spray burning legal system that utilizes involved by present embodiment makes the skeleton diagram of the fine-grain manufacturing apparatus of precursor particle.
Fig. 3 is the summary section employing the rechargeable nonaqueous electrolytic battery of positive active material involved by present embodiment.
Fig. 4 is the XRD of embodiment 1 and the positive active material involved by comparative example 1.
Fig. 5 (a) ~ (c) is the section SEM photo of the positive active material A involved by embodiment 1.
Fig. 6 (a) is the secondary electron image of the section SEM photo of positive active material A involved by embodiment 1, and (b) is the reflection electronic picture of same visual field.
Fig. 7 (a) is the SEM photo of the section of positive active material A involved by embodiment 1, and (b) ~ (e) is the EDS mapping graph of the carbon of same look-out station, oxygen, silicon, iron.
Fig. 8 (a) ~ (d) is the figure of the manganese concentration dependent representing the butane treatment time.
Embodiment
(positive active material)
Based on accompanying drawing, embodiments of the present invention are described in detail below.
Fig. 1 is the figure of the positive active material 1 represented involved by present embodiment.Positive active material 1, in silicic acid ferrimanganic lithium 3, at least comprises the particle 5 containing iron or cementite.And then except positive active material 1 at least comprises the particle 5 containing iron or cementite in silicic acid ferrimanganic lithium 3, also can there is particle 5 containing iron or cementite in the border between 1 particle of silicic acid ferrimanganic lithium 3 in positive active material 1.Positive active material 1 also can be the offspring that the particle of silicic acid ferrimanganic lithium 3 and particle 5 condense and obtain.The average grain diameter of offspring is about 0.5 ~ 20 μm, but is preferably about 5 ~ 15 μm.
Silicic acid ferrimanganic lithium 3 is with general formula Li 2fe 1-xmn xsiO 4(0.25≤x < 1) represents.
In addition, also can replace a part of Fe and/or Mn, be replaced at least one party of Co or Ni.
In addition, by replacing a part of Fe and/or Mn, also be replaced into Mg, Ca, Ti, V, Cr, Cu, Zn, Sr, Zr, Mo at least any one, thus except the effect of the increase of capacity and the increase of energy density, the stabilisation of crystal structure can also be realized, improve and recycle characteristic.
In addition, by replacing a part of Li, be replaced into Mg, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Zr, Mo at least any one, thus identical with preceding paragraph, can obtain the increase of capacity, the increase of energy density, crystal structure stabilisation, improve the effect recycling characteristic.
If utilize transmission electron microscope (TEM) Observe and measure particle diameter to the particle of silicic acid ferrimanganic lithium 3 and obtain the domain size distribution of 1 particle, then be preferably present in the scope of 10 ~ 200nm, average grain diameter is present in 25 ~ 100nm.In addition, domain size distribution is more preferably the scope of 10 ~ 150nm, and average grain diameter is present in 25 ~ 80nm.And so-called domain size distribution is present in the scope of 10 ~ 200nm, refer to that the domain size distribution of gained does not need to contain the four corner of 10 ~ 200nm, the lower limit of the domain size distribution of gained is more than 10nm, and the upper limit is below 200nm.That is, the domain size distribution of gained both can be 10 ~ 100nm, also can be 50 ~ 150nm.
In addition, also can by SiO 4a part utilize other anion metathesis.Be such as by the acid as transition metal, metatitanic acid (TiO 4) or chromic acid (CrO 4), vanadic acid (VO 4, V 2o 7), zirconic acid (ZrO 4), molybdic acid (MoO 4, Mo 7o 24), wolframic acid (WO 4) etc., or be by boric acid (BO 3), phosphoric acid (PO 4) displacement.By a part for silicate ion being utilized these anion kinds to replace, just contributing to suppressing by the deintercalation repeatedly of Li ion and restoring the changes in crystal structure that causes and realize stabilisation, service life cycle is improved.In addition, even if these anion kinds are at high temperature also difficult to discharge oxygen, therefore, it is possible to can not cause using safely with catching fire.
Particle 5 is containing iron (Fe) or cementite (Fe 3c) particle, can be only made up of iron or cementite, also can contain iron and cementite.Particle about particle 5 to be particle diameters be 100nm ~ 2 μm, about particle diameter is preferably 500nm ~ 1 μm.
Positive active material 1 preferably has carbon and is coated on surface.And then the powder conductivity with the positive active material 1 that carbon is coated to is preferably 10 -3more than S/cm.If the powder conductivity of positive active material 1 is 10 -3more than S/cm, then can obtain sufficient conductivity time in for positive pole.In addition, the content with the carbon in the positive active material 1 that carbon is coated to is preferably more than 1.5 % by weight.If the content of carbon is more than 1.5 % by weight, then powder conductivity also can uprise, and can obtain sufficient conductivity when being used in positive pole by positive active material.
Positive active material involved by present embodiment contains the silicic acid ferrimanganic lithium 3 of manganese with high concentration owing to comprising, therefore energy density is excellent.In addition, the positive active material involved by present embodiment, owing to having the particle 5 containing iron or cementite, is coated to therefore, it is possible to carry out sufficient carbon at short notice, excellent electric conductivity.
(positive electrode for nonaqueous electrolyte secondary battery)
Positive active material 1 can use as positive active material used in positive electrode for nonaqueous electrolyte secondary battery.Positive electrode for nonaqueous electrolyte secondary battery is formed in order to use positive active material 1, to in the powder of positive active material 1, also add the conductive auxiliary agents such as carbon black as required, and add polytetrafluoroethylene or Kynoar, the binding agents such as polyimides, the dispersants such as butadiene rubber, the thickeners such as carboxymethyl cellulose or other cellulose derivative, join in water system solvent or organic solvent and form slurries, by the material single or double of gained be coated on containing more than 95 % by weight aluminium the collector body such as alloy foil on, carry out burning till and solvent being volatilized solid.Thus, the positive electrode for nonaqueous electrolyte secondary battery of the active material layer containing positive active material can just be had on the current collector.
When the particle diameter of positive active material is little, in order to adaptation, the electrical collector of the coating and collector body and active material layer that improve slurries, also positive active material can be utilized the granulation such as spray drying process and carbon source.Although the block of the offspring of institute's granulation is the large block of about about 1 ~ 20 μm, will improve slurries coating thus, the characteristic of battery electrode and life-span also become better.Slurries used in spray drying process can use any one of water system solvent or non-water system solvent.
And then, be coated on by slurries containing positive active material in the positive pole that the collector body of alloy foil etc. is formed, 10 mean roughness Rz as collector body surface roughness regulation in Japanese Industrial Standards (JIS B 0601-1994) of active material layer forming surface are preferably more than 0.5 μm.The active material layer formed and the excellent adhesion of collector body, along with the electronic conductivity of the embedding deintercalation of Li ion and until the electrical collector of collector body increases, the service life cycle of discharge and recharge improves.
(rechargeable nonaqueous electrolytic battery)
In order to obtain the secondary cell of the high power capacity of the positive pole employing present embodiment, the various materials of negative pole or electrolyte, distance piece, the battery case etc. that make use of known negative electrode active material can be used without particular limitation.
Specifically, can with the rechargeable nonaqueous electrolytic battery 31 shown in Fig. 3 for exemplifying out.The rechargeable nonaqueous electrolytic battery 31 of present embodiment can be obtained by following operation, namely, positive pole 33, negative pole 35 are pressed from both sides across the order laminated configuration of distance piece 37 according to distance piece-negative pole-distance piece-positive pole, reel in the mode making positive pole 33 be in inner side and formed pole plate group, being inserted in battery can 41.In addition respectively positive pole 33 is connected with positive terminal 47 by positive wire 43, negative pole 35 is connected with battery can 41 by negative wire 45, the chemical energy that rechargeable nonaqueous electrolytic battery 31 inside produces externally can be derived as electric energy.Then, after fill electrolyte 39 with covering pole plate group in battery can 41, in the upper end (peristome) of battery can 41, the seal body 49 being formed, be built-in with relief valve mechanism by circular cover and the positive terminal 47 on its top therein installed by the insulating cell pressed from both sides across ring-type.
The capacity employing the secondary cell of positive pole involved by present embodiment is high, good electrode characteristic can be obtained, if and form secondary cell use non-aqueous matchmaker electrolyte in, use or add the non-aqueous matchmaker containing fluorine, even if repeatedly carrying out then through discharge and recharge, capacity is also difficult to reduce, and the life-span can extend.Such as, particularly when using the negative pole of negative electrode active material of the high power capacity containing silicon system, in order to suppress to remove by the doping of Li ion the large dilation caused that adulterates, preferably in the electrolytic solution use containing fluorine or alternatively base there is the electrolyte of the non-aqueous matchmaker of fluorine.When solvent containing fluorine can alleviate charging, particularly initial charging process time the volumetric expansion of the silicon system epithelium caused by the alloying with Li ion, therefore, it is possible to suppress the capacity caused by discharge and recharge to reduce.Fluorinated ethylene carbonate or fluoro linear carbonate etc. can be used in the non-aqueous matchmaker containing fluorine.List-tetrafluoro ethylene carbonate (4-fluoro-1 is had in fluorinated ethylene carbonate, 3-dioxolan-2-one, FEC), methyl 2 is had in fluoro linear carbonate, 2,2-trifluoroethyl carbonic ester, ethyl 2,2,2-trifluoroethyl carbonic esters etc., can by them individually or and use with multiple adding in electrolyte.Fluorine-basedly easily to be combined with silicon and firm, even if therefore also epithelium stabilisation can be made when the expansion caused by the charging alloying with Li ion, to be regarded as contributing to repression of swelling.
(manufacture method of the positive active material involved by present embodiment)
Positive active material involved by present embodiment can obtain by being burnt till by the presoma of silicic acid ferrimanganic lithium.The presoma of silicic acid ferrimanganic lithium utilizes the spray burning such as flame hydrolysis or thermal oxidation method method to synthesize.
And then, because the preferred surface carbon by positive active material is coated to, therefore preferred positive active material to be annealed under the atmosphere of appropriate hydrocarbon gas.
(manufacture method by the precursor particle of spray burning method)
(making of precursor particle)
Representing in fig. 2 utilizes spray burning legal system to make the example of the manufacturing installation of precursor particle.The reaction vessel of the fine-grain manufacturing apparatus 11 shown in Fig. 2 is configured with particulate synthesis nozzle 13 in container, supplies imflammable gas, combustion-supporting property gas and material solution in the flame produced by nozzle 13.On the other hand, there is the blast pipe 19 by generating particulate or reaction product discharge, utilizing particulate recovery filter 15 to reclaim the precursor particle 17 in being vented.
Spray burning method is following method, that is, utilize unstrpped gases such as supply chloride etc. method or by gasifier to the method for raw material liq or material solution, raw material supplying will be formed in flame together with imflammable gas with combustion-supporting property gas, make formation raw material reaction, obtain desired substance.As the suitable example of spray burning method, VAD (Vapor-phase Axial Deposition: vapor-phase axial deposition) method etc. can be enumerated.Although the temperature of these flames is according to the mixing ratio of imflammable gas and combustion-supporting property gas and form the interpolation ratio of raw material and change, but be usually between 1000 ~ 3000 DEG C, be particularly preferably about 1500 ~ 2500 DEG C, be more preferably about 1500 ~ 2000 DEG C.If flame temperature is low, then before the reaction likely in flame terminates, particulate is ejected into outside flame.In addition, if flame temperature is high, then the crystallinity of generated particulate is too high, in firing process thereafter, is stable phase but as the dissatisfactory phase of positive active material although easily generate.
In addition, flame hydrolysis will form the method for raw material hydrolysis in flame.In flame hydrolysis, generally use oxygen hydrogen flame as flame.To being supplied to hydrogen as imflammable gas, be supplied to the root of the flame of oxygen as combustion-supporting property gas side by side from the formation raw material of nozzle supply positive active material, flame raw material (oxygen and hydrogen) and synthesize desired substance.In flame hydrolysis, be in inert gas and fill in atmosphere, the particulate of nano level atomic desired substance that is little, that form primarily of noncrystalline can be obtained.
In addition, so-called thermal oxidation method will form the method for raw material thermal oxidation in flame.In thermal oxidation method, generally use hydrocarbon flame as flame.While to being supplied to hydrocarbon system gas as imflammable gas, being supplied to the root of the flame of air as combustion-supporting property gas, side by side form raw material and flame raw material (such as propane gas and oxygen) from nozzle supply, synthesize desired substance.As hydrocarbon system gas, the olefin-based appropriate hydrocarbon gas such as paraffin series appropriate hydrocarbon gas, ethene, propylene, butylene such as methane, ethane, propane, butane can be used.
(for obtaining the formation raw material of precursor particle)
Lithium source, source of iron, manganese source, silicon source for obtaining the formation raw material of the precursor particle of present embodiment.When raw material is solid, directly supply powder, or be scattered in liquid or be dissolved in make solution in solvent after be given to flame by gasifier.When raw material is liquid, except by except gasifier, gasifies after heating or decompression and bubbling can also be utilized before supply nozzle to improve vapour pressure and supply.Particularly, preferably the mixed solution in lithium source, source of iron, manganese source, silicon source is supplied with the vaporific drop of diameter less than 20 μm.
As lithium source, the organo-lithium compound, lithia, lithium peroxide etc. of beta-diketon base (diketonato) compound of the lithium alkoxide such as lithium acylate, lithium ethoxide such as the lithium inorganic acid salts such as lithium chloride, lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium bromide, lithium phosphate, lithium sulfate, lithium oxalate, lithium acetate, aphthenic acids lithium, lithium etc. can be used.And so-called aphthenic acids, the mixture of the different carboxylic acid that the multiple acidic materials mainly in oil are obtained by mixing, principal component is the carboxylic acid compound of pentamethylene and cyclohexane.
As source of iron, iron chloride, ferric oxalate, ferric acetate, ferrous sulfate, ferric nitrate, iron hydroxide, 2 ethyl hexanoic acid iron, iron naphthenate etc. can also be used according to condition.And then, the organic metal salt, iron oxide etc. of the iron of stearic acid, dimethyl dithiocarbamic acid, acetylacetonate, oleic acid, linoleic acid, leukotrienes etc. can also be used according to condition.
As manganese source, manganese chloride, manganese oxalate, manganese acetate, manganese sulfate, manganese nitrate, oxygen manganous hydroxide, 2 ethyl hexanoic acid manganese, manganese naphthenate, caproic acid manganese etc. can also be used according to condition.And then, the organic metal salt, manganese oxide etc. of the manganese of stearic acid, dimethyl dithiocarbamic acid, acetylacetonate, oleic acid, linoleic acid, leukotrienes etc. can also be used according to condition.
As silicon source, silicon tetrachloride can be used, octamethylcy-clotetrasiloxane (OMCTS), the hydrate of silicon dioxide or silicon monoxide or these silica, orthosilicic acid or metasilicic acid, the condensation silicic acid of inclined two silicic acid etc., tetraethyl orthosilicate (tetraethoxysilane, TEOS), tetramethyl orthosilicate (tetramethoxy-silicane, TMOS), methyltrimethoxy silane (MTMS), methyl triethoxysilane (MTES), HMDO (HMDSO), tetramethyl disiloxane (TMDSO), tetramethyl-ring tetrasiloxane (TMCTS), octamethyltrisiloxane (OMTSO), four n-butoxy silane etc.
In addition, when a part for the silicic acid by silicic acid ferrimanganic lithium utilizes other anion metathesis, as negative ion source, the raw material of the oxide of transition metal, boric acid, phosphoric acid is added.
Such as, titanium oxide can be used respectively according to required negative ion source and synthesis condition, the sub-titanous such as iron titanate or sub-manganese titanate acid metal salt, zinc titanate or magnesium titanate, the titanates such as barium titanate, vanadium oxide, ammonium metavanadate, chromium oxide, chromate or two chromate, manganese oxide, permanganate or manganate, cobaltatess, zirconia, zirconates, molybdenum oxide, molybdate, tungsten oxide, tungstates, boric acid or diboron trioxide, kodalk or sodium tetraborate, the various borate such as borax, phosphorous acid, the phosphoric acid of former phosphoric acid or metaphosphoric acid etc., diammonium hydrogen phosphate, the ammonium hydrogen phosphate salt etc. such as ammonium dihydrogen phosphate.
These raw materials are supplied to together with flame raw material same reaction be and synthesize precursor particle.Filter can be utilized from Exhaust Gas to reclaim the precursor particle generated.In addition, also can make it as shown below to be created on around plug.The plug (being also referred to as kind of a rod) of silicon dioxide or silicon system is set in the reactor, when supplying in lithium source, source of iron, manganese source, silicon source to the oxygen hydrogen flame blowed it or in propane flame together with flame raw material, when making it hydrolysis or oxidation reaction, mainly will generate the particulate of attachment nanometer scale at mandrel surface.Reclaim these and generate particulate, according to circumstances use filter or sieve, remove impurity or condense thick composition.Precursor particle obtained like this has nano level atomic little particle diameter, forms primarily of belonging to amorphous particulate.
The precursor particle that the manufacture method of the precursor particle involved by present embodiment and spray burning method can manufacture is noncrystalline, and the size of particle is also very little.And then, in spray burning method, compared with hydrothermal synthesis method in the past or solid phase method, can synthesize in a large number at short notice, uniform precursor particle can be obtained at low cost.
(feature of the precursor particle utilizing spray burning method to obtain)
In the present invention, burn till by precursor particle is mixed with reducing agent, thus can positive active material be obtained.So-called presoma in present embodiment is the material of the crystal that can obtain silicic acid ferrimanganic lithium by burning till.Particularly, although the valence mumber that the presoma in present embodiment is iron or manganese is 3 valencys and for noncrystal, burn till, thus the valence mumber of iron or manganese becomes divalent from 3 valencys by mixing with reducing agent.The composition of precursor particle preferably meets stoichiometric composition.
In addition, the shape of precursor particle is almost spherical, and the average aspect ratio (major diameter/minor axis) of particle is less than 1.5, is preferably less than 1.2, is more preferably less than 1.1.And so-called particle is almost spherical, do not refer to that shape of particle is strict spherical or oval spherical geometrically, even if there is small jut, as long as the surface of particle is made up of roughly smooth curved surface.
When measuring the powder method X-ray diffraction of scope of 2 θ=10 ~ 60 ° to these precursor particle, substantially not there is diffraction maximum, even if or have diffraction maximum also very little, demonstrate the roomy angle of diffraction.That is, precursor particle is made up of microcrystal little particulate or the polycrystalline particulate of assembling little monocrystalline, or around these particulates, there is the crystallite form of noncrystalline composition.
In the spray burning method of present embodiment, because carbon burns in flame, therefore in the precursor particle of gained, do not contain carbon.Even if suppose to be mixed into carbon component, be also denier, not reach in positive pole time the amount of degree of conductive auxiliary agent.
(manufacture of positive active material)
After the precursor particle utilizing spray burning method to obtain is mixed with carbon source again, burn till under inert gas fills atmosphere, just can obtain positive active material thus.Amorphous compound contained in precursor particle or the mixture of oxide form mainly become the compound of the crystal habit of the silicic acid ferrimanganic lithium system of olivine structural owing to burning till.Now, a part for the ferrous components contained in presoma when burning till is restored to the metallic state of zeroth order, separates out the particle 5 containing iron or cementite.
In addition, under inert gas fills atmosphere, carbon source burning and positive active material oxidation when burning till can be prevented.As inert gas, nitrogen, argon gas, neon, helium, carbon dioxide etc. can be used.In order to improve the conductivity of the product after burning till, the conductive carbon such as the carbohydrate of polymer, the sucrose etc. such as the polyalcohols such as polyvinyl alcohol, PVP, carboxymethyl cellulose, acetylcellulose, carbon black being joined after in precursor particle as carbon source before burning till and burns till.Because polyvinyl alcohol not only plays a role as the adhesive of the precursor particle before burning till, but also in burning till, iron or manganese can be reduced well, therefore particularly preferably.
If firing condition is the combination in temperature 300 ~ 900 DEG C and 0.5 ~ 10 hour processing time, then can obtain required crystallinity and the burned material of particle diameter rightly.Due to high temperature or burn till caused excessive heat load for a long time and may generate thick monocrystalline, therefore should avoid, preferably under the heating condition of degree that can obtain required crystallinity or microcrystalline silicic acid ferrimanganic lithium, can the firing condition of the size of microcrystal as much as possible.Firing temperature is preferably about 400 ~ 700 DEG C.
(annealing by appropriate hydrocarbon gas)
After formation positive active material is burnt till in utilization, anneal in appropriate hydrocarbon gas, form carbon on the surface of positive active material and be coated to.
Temperature during annealing is preferably 600 DEG C ~ 750 DEG C.This is because if annealing temperature is too low, then carbon is slow from the precipitation appropriate hydrocarbon gas, if too high, then crystal can too greatly grow.
It is one kind or two or more that appropriate hydrocarbon gas is preferably selected from methane, ethane, propane, butane.Although appropriate hydrocarbon gas also has reproducibility, but in order to advance reduction further, also supply reducibility gas can be mixed.
It is one kind or two or more that reducibility gas is preferably selected from hydrogen, acetylene, carbon monoxide, hydrogen sulfide, sulfur dioxide, formaldehyde.
Utilization annealing, appropriate hydrocarbon gas is reacted with the particle 5 containing iron or cementite, and appropriate hydrocarbon gas is decomposed, combination, can carry out carbon be coated to the surface of positive active material.
And, because the positive active material of gained often can condense in firing process or annealing operation, therefore, it is possible to by using mortar or ball mill or other disintegrating mechanism, again make particulate.
(feature of present embodiment)
According to the present embodiment, owing to using spray burning method, therefore, it is possible to continuously and synthesize the precursor particle of positive active material on a large scale.
In addition, the positive active material involved by present embodiment is coated to owing to can carry out carbon at short notice on the surface of the particle of the silicic acid ferrimanganic lithium of capacity excellence, therefore, it is possible to be applied to fully by silicic acid ferrimanganic lithium in discharge and recharge reaction.
Embodiment
Below, although utilize embodiment, the present invention will be described, but the present invention is not by any restriction of the present embodiment.
(1-1) synthesis example 1
(Li 2fe 0.75mn 0.25siO 4the making of precursor particle)
Representing in fig. 2 utilizes spray burning legal system to make the manufacturing installation of precursor particle.In the reaction vessel of the device in fig. 2, use propane gas (C as imflammable gas 3h 8), use air (Air) as combustion-supporting property gas, material solution is supplied to flame from nozzle 13.On the other hand, there is the blast pipe by generating particulate or reaction product discharge, utilizing particulate recovery filter 15 to reclaim the precursor particle 17 in being vented.The kind and the supply conditions that are supplied to the raw material of nozzle are as follows.In addition, to make the size of drop be the mode of 20 μm, use second fluid nozzle base feed solution in flame.The temperature of flame is about 2000 DEG C.
Imflammable gas: propane (C 3h 8): 1dm 3/ min
Combustion-supporting property gas: air: 5dm 3/ min
Lithium source: LiCl (lithium chloride, the 4M aqueous solution): 0.2dm 3/ min
Source of iron: FeCl 24H 2o (frerrous chloride, the 1M aqueous solution): 0.075dm 3/ min
Manganese source: MnCl 24H 2o (manganese chloride, the 1M aqueous solution): 0.025dm 3/ min
Silicon source: SiCl 4(silicon tetrachloride): 0.1dm 3/ min
Utilize the manufacture method of the precursor particle of spray burning method as follows.First, N is supplied quantitatively 2gas, is set to inert gas atmosphere by reaction vessel.Under such a condition, by be mixed with respectively lithium source, source of iron, manganese source solution to be made the drop of 20 μm by atomizer, be supplied to flame with propane gas, air together with silicon tetrachloride.The precursor particle particulate recovery filter of the mixture of the particulate of the particulate as lithia, iron oxide, phosphorous oxides etc. generated in flame, silicic acid ferrimanganic lithium etc. is reclaimed.The precursor particle of gained is precursor particle a.
(1-2) synthesis example 2
(Li 2feSiO 4the making of precursor particle)
In addition, identical with synthesis example 1, utilize spray burning method, the material solution of supplying propane gas, air and following normal concentration in the flame of propane gas, by making it thermal oxidation thus synthesizing and collect precursor particle b.
Imflammable gas: propane (C 3h 8): 1dm 3/ min
Combustion-supporting property gas: air: 5dm 3/ min
Lithium source: aphthenic acids lithium (4M solution): 0.2dm 3/ min
Source of iron: C 16h 30feO 4(2 ethyl hexanoic acid iron (II), iron octoate) (1M solution): 0.1dm 3/ min
Silicon source: octamethylcy-clotetrasiloxane: 0.1dm 3/ min
(2-1) embodiment 1
To in the precursor particle a of silicic acid ferrimanganic lithium, add with reaching the 10wt% of powder polyvinyl alcohol and mixing after, at N 2under gas atmosphere, at 250 DEG C, carry out 4 hours temporarily burn till, then at 650 DEG C, carry out 8 hours formally burn till.Occur in burning till temporarily polyvinyl alcohol melting and to the infiltration in powder, in formally burning till, there is the carbonization of polyvinyl alcohol and the reduction of iron and manganese, generate silicic acid ferrimanganic lithium and the particle containing iron or cementite.
Thereafter, while making butane circulate, at 650 DEG C, the annealing of 10 minutes is carried out.Implement to the carbon coating or carbon-supported on positive active material.
Pulverization process is carried out to the agglomerate of gained, obtains positive active material A.
(2-2) comparative example 1
To in the precursor particle a of silicic acid ferrimanganic lithium, add with reaching the 3wt% of powder polyvinyl alcohol and mixing after, at N 2under gas atmosphere, at 250 DEG C, carry out 4 hours temporarily burn till, then at 650 DEG C, carry out 8 hours formally burn till.Occur in burning till temporarily polyvinyl alcohol melting and to the infiltration in powder, in formally burning till, there is the carbonization of polyvinyl alcohol and the reduction of iron and manganese, generate silicic acid ferrimanganic lithium.In comparative example 1, there is no the particle generated containing iron or cementite.
Thereafter, while making butane circulate, at 650 DEG C, the annealing of 10 minutes is carried out.Implement to the carbon coating or carbon-supported on positive active material.
Pulverization process is carried out to the agglomerate of gained, obtains positive active material B.
(2-3) comparative example 2
To in the precursor particle b of silicic acid ferrimanganic lithium, add with reaching the 3wt% of powder polyvinyl alcohol and mixing after, at N 2under gas atmosphere, at 250 DEG C, carry out 4 hours temporarily burn till, then at 650 DEG C, carry out 8 hours formally burn till.Occur in burning till temporarily polyvinyl alcohol melting and to the infiltration in powder, in formally burning till, there is the carbonization of polyvinyl alcohol and the reduction of iron, generate ferric metasilicate lithium.In comparative example 2, there is no the particle generated containing iron or cementite.
Thereafter, while making butane circulate, at 650 DEG C, the annealing of 10 minutes is carried out.Implement to the carbon coating or carbon-supported on positive active material.
Pulverization process is carried out to the agglomerate of gained, obtains positive active material C.
(3) evaluation of sample
(3-1) X-ray diffraction (XRD)
Fig. 4 is X-ray diffraction (XRD) figure of the positive active material A involved by the embodiment 1 and positive active material B involved by comparative example 1.The K alpha ray of Cu is make use of in x-ray source.The known silicic acid ferrimanganic lithium all generating olivine structural.In addition, in embodiment 1, near 45 degree, observe the peak in (1,1, the 0) face coming from iron.
(3-2) scanning electron microscope (SEM) of section is observed
Positive active material A on aluminium foil with carbon black together with Kynoar involved by coating Examples 1 and form active material layer, utilizes SEM to observe and utilizes ion to grind the section of the active material layer exposed.
Fig. 5 (a) ~ (c) is the SEM photo of the section representing positive active material A.In Fig. 5 (a), can observe and comprise the particle of silicic acid ferrimanganic lithium 3 and the particle 5 i.e. positive active material of offspring containing iron or cementite as primary particle.Shinny particle in Fig. 5 (a) is the particle 5 containing iron or cementite, and its particle diameter is about 500nm.Fig. 5 (b) observes the SEM photo being different from the visual field of Fig. 5 (a).Shinny particle is the particle 5 containing iron or cementite, and its particle diameter is about 1 μm.Fig. 5 (c) observes the SEM photo being different from the visual field of Fig. 5 (a).Shinny particle is the particle 5 containing iron or cementite, and its particle diameter is about 1 μm.
Fig. 6 (a), (b) are the SEM photos of the section representing positive active material A, and Fig. 6 (a) is secondary electron image, and (b) is the reflection electronic picture of same field.Obfuscation in Fig. 6 (a), particle shinny in Fig. 6 (b) are the particles 5 containing iron or cementite, and its particle diameter is about 300nm ~ 500nm.
(3-3) by the composition analysis of EDS
Use scanning transmission electron microscope, utilize EDS (Energy Dispersive Spectroscopy: energy dispersion type X-ray analysis) to analyze the composition analysis of the positive active material A carried out involved by embodiment 1.Fig. 7 (a) is the section SEM photo of the positive active material A involved by embodiment 1, and Fig. 7 (b) ~ (e) is the EDS mapping graph of the carbon of same look-out station, oxygen, silicon, iron.Utilize the method identical with Fig. 5 that section is exposed.
In Fig. 7 (a), observe the granulation body of the positive active material of particle diameter about 8 μm, positive active material is condensed and form positive active material the particle of the silicic acid ferrimanganic lithium of particle diameter about 200nm ~ 500nm, the particle 5 containing iron or cementite that to be about 1 μm with particle shape.In Fig. 7 (b), around positive active material, detect that carbon is coated to or comes from the carbon of conductive agent and carbon black.In Fig. 7 (c) and (d), detect oxygen and the silicon of the silicic acid ferrimanganic lithium coming from positive active material.In Fig. 7 (e), in (a), detect the iron coming from shinny particle 5.
(3-4) evaluation of powder conductivity
In order to evaluate the electronic conductivity be under powder state, the powder resistance Analytical system MCP-PD51 type of Mitsubishi Chemical is used to carry out the evaluation of powder conductivity.Powder conductivity is that the resistance value obtained is obtained according to measuring the sample powder that have compressed with the pressure of 4MPa.
Positive active material involved by embodiment 1 is owing to having the particle containing iron or cementite, and the powder conductivity therefore after the butane treatment of 10 minutes is up to 2 × 10 -1s/cm.This powder conductivity is with the powder conductivity of the positive active material C of the comparative example 2 obtained not carrying out butane treatment containing the ferric metasilicate lithium of manganese 1 × 10 -1the conductivity that S/cm is equal.On the other hand, the positive active material B involved by comparative example 1 is not owing to having the particle containing iron or cementite, and the non-constant of powder conductivity therefore after the butane treatment of 10 minutes is 1 × 10 -7s/cm.
And, if carry out the butane treatment of 60 minutes to the positive active material involved by comparative example 1, then have 3 × 10 -1the conductivity of about S/cm.That is, the particle containing iron or cementite plays the effect promoting carbon from the precipitation appropriate hydrocarbon gas.
(3-5) evaluation of carbon content
To the embodiment 1 of butane treatment, the positive active material A ~ C of comparative example 1 ~ 2 that have carried out 10 minutes, burning infrared absorption is utilized to carry out the mensuration of carbon content respectively.Consequently, being 2.0 % by weight in the positive active material A involved by embodiment 1, is 1.4 % by weight in the positive active material B involved by comparative example 1, is 2.6 % by weight in the positive active material C involved by comparative example 2.According to this result, in the embodiment 1 comprising the particle containing iron or cementite, separate out the carbon with comparative example 1 same degree of ferric metasilicate lithium.
Above, while reference accompanying drawing, although be preferred embodiment illustrated of the present invention, but the present invention is not limited to this example.Obviously, as long as those skilled in the art, just in the category of disclosed technological thought in this application, various modification or fixed case can be expected, should be appreciated that they also belong to technical scope of the present invention certainly.
The explanation of Reference numeral
1 ... positive active material
3 ... silicic acid ferrimanganic lithium
5 ... particle
11 ... fine-grain manufacturing apparatus
13 ... particulate synthesis nozzle
15 ... particulate recovery filter
17 ... precursor particle
19 ... blast pipe
31 ... rechargeable nonaqueous electrolytic battery
33 ... positive pole
35 ... negative pole
37 ... distance piece
39 ... electrolyte
41 ... battery can
43 ... positive wire
45 ... negative wire
47 ... positive terminal
49 ... seal body

Claims (16)

1. a positive active material, is characterized in that,
With general formula Li 2fe 1-xmn xsiO 4in the silicic acid ferrimanganic lithium that (0.25≤x < 1) represents, comprise the particle containing iron or cementite.
2. positive active material according to claim 1, is characterized in that,
Replace a part of Fe and/or Mn, be replaced at least one party of Co or Ni.
3. positive active material according to claim 1, is characterized in that,
Replace a part of Fe and/or Mn, be replaced into Mg, Ca, Ti, V, Cr, Cu, Zn, Sr, Zr, Mo at least any one.
4. positive active material according to claim 1, is characterized in that,
Replace a part of Li, be replaced into Mg, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Zr, Mo at least any one.
5. positive active material according to claim 1, is characterized in that,
Border between the particle of silicic acid ferrimanganic lithium, has the particle containing iron or cementite.
6. positive active material according to claim 1, is characterized in that,
It comprises the particle of described silicic acid ferrimanganic lithium and the described offspring containing the particle of iron or cementite.
7. positive active material according to claim 1, is characterized in that,
There is on the surface of described positive active material carbon be coated to.
8. positive active material according to claim 7, is characterized in that,
Powder conductivity is 10 -3more than S/cm.
9. positive active material according to claim 7, is characterized in that,
The content of the carbon in described positive active material is more than 1.5 % by weight.
10. positive active material according to claim 1, is characterized in that,
The described average grain diameter containing the particle of iron or cementite is 100nm ~ 2 μm.
11. 1 kinds of positive electrode for nonaqueous electrolyte secondary battery, is characterized in that,
Have: collector body and be positioned at described collector body at least one side containing the positive electrode active material layer of positive active material according to claim 1.
12. 1 kinds of rechargeable nonaqueous electrolytic batteries, is characterized in that,
There is positive electrode for nonaqueous electrolyte secondary battery according to claim 11, the negative pole store and discharge lithium ion and the distance piece be configured between described positive pole and described negative pole can be inhaled, in the electrolyte with lithium-ion-conducting, be provided with described positive pole, described negative pole and described distance piece.
13. 1 kinds comprise with general formula Li 2fe 1-xmn xsiO 4the manufacture method of the positive active material of the silicic acid ferrimanganic lithium that (0.25≤x < 1) represents and the particle containing iron or cementite, is characterized in that possessing:
Lithium source, source of iron, manganese source and silicon source is used to synthesize the operation (a) of precursor particle; The operation (b) of mixed carbon source in described precursor particle; And by operation (c) that the described precursor particle be mixed with described carbon source is burnt till under an inert atmosphere.
The manufacture method of 14. positive active materials according to claim 13, is characterized in that,
After described operation (c), also possesses the operation (d) of being annealed under appropriate hydrocarbon gas atmosphere by described positive active material.
The manufacture method of 15. cathode active material according to claim 13, is characterized in that,
In described operation (a), described lithium source, described source of iron, described manganese source and described silicon source are supplied in flame with combustion-supporting property gas with vaporific drop together with imflammable gas, synthesis particle mixture.
The manufacture method of 16. positive active materials according to claim 13, is characterized in that,
Described carbon source is more than any one of polyvinyl alcohol, PVP, carboxymethyl cellulose, acetylcellulose, sucrose and carbon black.
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Application publication date: 20150909