CN107534148A - Ion secondary battery cathode material lithium carbonaceous coated graphite particle, lithium ion secondary battery negative pole and lithium rechargeable battery - Google Patents

Ion secondary battery cathode material lithium carbonaceous coated graphite particle, lithium ion secondary battery negative pole and lithium rechargeable battery Download PDF

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Publication number
CN107534148A
CN107534148A CN201680025230.0A CN201680025230A CN107534148A CN 107534148 A CN107534148 A CN 107534148A CN 201680025230 A CN201680025230 A CN 201680025230A CN 107534148 A CN107534148 A CN 107534148A
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lithium
carbonaceous
ion secondary
graphite particle
graphite
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CN201680025230.0A
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CN107534148B (en
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间所靖
江口邦彦
盐出哲夫
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JFE Chemical Corp
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JFE Chemical Corp
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Priority claimed from PCT/JP2016/002602 external-priority patent/WO2016194355A1/en
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/36—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
    • 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

Abstract

The present invention provides the negative material that excellent battery behavior can be obtained when for ion secondary battery cathode material lithium.A kind of ion secondary battery cathode material lithium graphite particle, it has carbonaceous coated graphite plasmid of carbonaceous material at least a portion on the surface that the graphite particle that anisotropy pressurization is formed is carried out to spherical and/or ellipsoid shaped graphite, and the carbonaceous coated graphite plasmid overabundance of amniotic fluid foot states (1)~(3).(1) mass parts of graphite particle 100 that the content of the carbonaceous material is formed relative to the carry out anisotropy pressurization in carbonaceous coated graphite plasmid are 0.1~3.0 mass parts.(2) be below 0.100mL/g using the pore volume below 1.1 μm of the fine pore of mercury injection apparatus measure, and the pore volume below 0.54 μm of fine pore is more than 80% relative to the ratio of the pore volume below 1.1 μm of the fine pore.(3) dibutyl phthalate (DBP) oil absorption is below 40.0mL/100g.

Description

Ion secondary battery cathode material lithium carbonaceous coated graphite particle, lithium ion secondary GND and lithium rechargeable battery
Technical field
Used the present invention relates to ion secondary battery cathode material lithium carbonaceous coated graphite particle, lithium rechargeable battery negative Pole and the lithium rechargeable battery using the negative pole.
Background technology
Lithium rechargeable battery is equipped in portable electric appts extensively, also begin to be used in hybrid vehicle, In electric automobile.In such situation, lithium rechargeable battery is required better high power capacity, high speed charge-discharge characteristic, Cycle characteristics.
Lithium rechargeable battery is using negative pole, positive pole and nonaqueous electrolyte as main inscape, by making lithium ion Migrate between negative pole and positive pole in discharge process and charging process and played a role as secondary cell.At present, it is above-mentioned negative Pole material widely uses graphite.Graphite is roughly divided into native graphite and Delanium.Native graphite has crystallinity height, capacity high The advantages of, but due to scale shape, particle is orientated in one direction in electrode, high speed charge-discharge characteristic, circulation be present The shortcomings that characteristic difference.
In order to make up the shortcoming, it is proposed that largely implement the machining graphite glomeration of scale shape and further surface Material obtained from cladding processing.The surface of native graphite after nodularization, which is exposed, much reactive high sides with electrolyte Edge face, the purpose of cladding are to seal and suppress side reaction the edge surface.In recent years, with maximization of portable equipment etc., It is required that the further high-energy-density of battery, accompanies with this, further densification is also required to for negative pole.But In conventional coated natural graphite, the intensity of clad is insufficient, is cracked in clad, is cracked due to densification Deng, as a result, the problem of reduction such as starting efficiency, cycle characteristics be present.
On the other hand, Patent Document 1 discloses a kind of manufacture method of ion secondary battery cathode material lithium, its feature exists In to ball graphite progress isotropism pressurization.In addition, Patent Document 2 discloses a kind of lithium rechargeable battery stone Ink material, it is characterised in that obtained carrying out pressurized treatments to native graphite nodularization particle and/or native graphite consolidated block particle The surface of the pressurization graphite particle arrived is formed with the clad comprising carbide.
These documents illustrate：As using effect of the high graphite particle of high density, isotropism as negative material, Under same negative pole density, the space between graphite particle broadens, therefore, it is possible to improve the logical fluidity of electrolyte, in addition, even if entering Row is compressing to make negative pole, and the crystalline texture of graphite is not easy to be orientated, will not damage the logical fluidity of electrolyte.
But present situation is, even if using these methods, the improved effect of battery performance can not say it is sufficient.
Prior art literature
Patent document
Patent document 1：No. 4499498 publications of Japanese Patent No.
Patent document 2：Japanese Unexamined Patent Publication 2011-60465 publications
The content of the invention
Invent problem to be solved
The present invention is to complete in view of the above circumstances.That is, its object is to provide even in for lithium ion secondary Also the negative material of excellent battery behavior can be obtained in the case of cell negative electrode material.In addition, its object is to provide this The manufacture method of negative material, the negative pole using the negative material and the lithium rechargeable battery using the negative pole.It is here, excellent Battery behavior refer to high discharge capacity, high first efficiency for charge-discharge, high high speed charge-discharge characteristic and excellent circulation Characteristic.
For solving the method for problem
The present invention is a kind of carbonaceous coated graphite particle of ion secondary battery cathode material lithium, it is characterised in that its Be using spherical or ellipsoid shaped graphite particle as core, the core is carries out the graphite core that is formed of anisotropy pressurization And at least a portion on the surface of the core has the carbonaceous coated graphite particle for the clad being made up of carbonaceous.
The negative pole of lithium rechargeable battery is suppressed in its manufacturing process in order to realize designed electrode density Shaping.Generally, this it is compressing use roll squeezer, anisotropic pressure is applied to the negative material for forming electrode.The present invention It is conceived to this point and completes, i.e. by implementing anisotropic pressurized treatments to negative material in advance, when suppresses to make negative pole The compressing caused deformation of particle and the damage of the clad associated with this, even if making electrode density be high density, Also high first efficiency for charge-discharge, high speed charge-discharge characteristic and cycle characteristics are able to maintain that.
Invention effect
The carbonaceous coated graphite particle of the present invention meets good electric discharge as ion secondary battery cathode material lithium Capacity, first efficiency for charge-discharge, high speed charge-discharge characteristic and cycle characteristics.Therefore, formed using the negative material of the present invention Lithium rechargeable battery meet the expectation of the high-energy densification to battery in recent years, for the small-sized of the equipment carried Change and high performance is useful.
Brief description of the drawings
Fig. 1 is the sectional drawing for the evaluation battery evaluated for the battery behavior of the negative pole to the present invention.
Embodiment
Hereinafter, the present invention is more specifically illustrated.
1. graphite particle
[spherical and/or ellipsoid shaped graphite]
The raw material of the graphite particle of the present invention is put down using spherical or ellipsoid shaped 1~50 μm of average grain diameter, preferably Equal draw ratio is below 5, the graphite particle of the μ m of average grain diameter 5~30.More preferably average aspect ratio below 2, average specific table Area 10m2/ below g, particularly preferably 8m2/ below g.
The processing glomeration of commercially available product or the native graphite particle of ellipsoid shaped can also be used.In spherical or ellipsoid shaped It is in the case of the native graphite of shape in addition, such as flaky graphite particle, natural flaky graphite is outer using machinery Power be granulated nodularization and globular graphite particle is made.The method of processing glomeration or ellipsoid shaped can be enumerated for example：In glue The method that multiple flaky graphites is mixed under the coexisting of granulation aid such as stick or resin, machine is applied to multiple flaky graphites Tool external force and be applied in combination without using the method for adhesive, two methods.But most preferably applied without using granulation aid Mechanical external force is added to be granulated glomerate method.Mechanical external force refers to mechanically be crushed and be granulated, can be by flakey Graphite is granulated and carries out nodularization.As the reducing mechanism of flaky graphite, it can use and be mixed such as pressure kneader, twin-roll machine Mill, rotating ball mill, カ ウ Application タ ジ ェ ッ ト ミ Le (counter-jet mill) (the thin close Krona Co., Ltd. manufacture in river), カ レ Application ト The reducing mechanisms such as ジ ェ ッ ト (day clear エ Application ジ ニ ア リ Application グ Co., Ltd. manufacture).
The surface of above-mentioned pulverized product has the part of acute angle, therefore, is used after pulverized product being carried out into granulation nodularization.Make For the granulation spheroidization device of pulverized product, such as GRANUREX (manufacture of Off ロ イ Application ト Industry Co., Ltd), ニ ュ can be used ー グ ラ マ シ Application (K. K. Kiyoarata Enterprise), ア グ ロ マ ス タ ー (the thin close Krona Co., Ltd. manufacture in river) etc. are granulated Machine, Ha イ Block リ ダ イ ゼ ー シ ョ Application (hybrid system) (Nara Machinery Co., Ltd.'s manufacture), メ カ ノ マ イ Network ロ ス (Nara Machinery Co., Ltd.'s manufacture), (thin river is close for メ カ ノ フ ュ ー ジ ョ Application シ ス テ system (mechanical fusion system) The manufacture of Krona Co., Ltd.) etc. shearing compression process device.
Lc as the measured value of the X-ray diffraction of the graphite particle of the present invention is preferably that more than 40nm, La are preferably More than 40nm.Here, Lc is the size Lc (002) of the crystallite in the c-axis direction of graphite-structure, La is the big of the crystallite of a direction of principal axis Small La (110).It is preferred that d002 is below 0.337nm, the 1360cm determined by using the Raman spectroscopy of argon laser-1Peak intensity Spend (I1360) and 1580cm-1Peak intensity (I1580) the ratio between I1360/I1580(R values) is 0.06~0.30 and 1580cm-1Bands of a spectrum Half-peak a width of 10~60.
[the graphite particle for carrying out anisotropy pressurization and being formed]
The graphite particle of the present invention to above-mentioned spherical or ellipsoid shaped graphite by carrying out anisotropy pressurization to be formed. As a result, graphite particle of the invention have the direction upper density that carries out anisotropy pressurization it is high, in its right angle orientation it is close Spend low orientation.
Below the 500nm using mercury injection method measure of the graphite particle of the present invention pore volume of size is preferably Below 0.100mL/g or using 100~200nm of mercury injection method measure size pore volume be preferably 0.02mL/g with Under.During more than the scope, binding material when making negative pole is penetrated into the pore, and stripping electrode intensity may reduce.
2. carbonaceous coated graphite particle
The ion secondary battery cathode material lithium of the present invention carries out anisotropy with carbonaceous coated graphite particle in above-mentioned At least a portion on the surface for the graphite particle for pressurizeing and being formed has carbonaceous material.That is, the surface of the graphite particle At least a portion is coated by carbonaceous material.Its manufacture method does not limit, preferably using carbonaceous precursor as raw material, by described later Manufacture method is coated at least a portion on the surface of graphite particle using carbonaceous material.As used carbonaceous material The precursor of material, tar asphalt class and/or resinae can be illustrated.Specifically, can as mink cell focus, particularly tar asphalt class To enumerate oil in coal tar, tar light oil, tar, the drip of tar heavy oil, naphtalene oil, carbolineum, coal tar asphalt, coal tar, interphase Blue or green, oxygen bridge connects asphalt, heavy oil etc..As resinae, the thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, phenol can be illustrated The thermosetting resins such as urea formaldehyde, furane resins.It is to have in cost when being only set to tar asphalt class it is preferred that being free of resinae Profit.The precursor of carbonaceous material can use foregoing illustrative any material, but particularly preferably coal tar asphalt is 80 mass % More than.
In the carbonaceous coated graphite particle of the present invention, the content of carbonaceous material is relative to the stone in carbonaceous coated graphite particle Sub 100 mass parts of black plasmid are 0.1~3.0 mass parts.When the content of carbonaceous material is less than 0.1 mass parts, it is difficult to cladding completely The graphite edge surface of activity, first efficiency for charge-discharge reduce sometimes.When on the other hand, more than 3.0 mass parts, discharge capacity is relative The ratio of relatively low carbon material is too high, and the discharge capacity of carbonaceous coated graphite particle reduces.In addition, for forming carbonaceous material When the ratio of raw material (type thermosetting resin, tar asphalt class) is more, in cladding process, heat treatment step afterwards, particle holds Easily fusion, a part for the layer of carbonaceous material for the carbonaceous coated graphite particle for making to finally give are cracked, peeled off, produce sometimes The reduction of initial charge/discharge efficiency.The content of carbonaceous material is relative to the matter of graphite particle 100 in carbonaceous coated graphite particle Amount part is preferably 0.3~3.0 mass parts, more preferably 1.0~3.0 mass parts.It should be noted that carbonaceous material contains Measure by carbonaceous coated graphite particle it is overall be averaged in terms of within the above range.Each particle is not needed all in above range It is interior, the particle beyond some above range can be contained.
In addition, the pore below 1.1 μm of the fine pore using mercury injection apparatus measure of the carbonaceous coated graphite particle of the present invention Volume is below 0.100mL/g, and the pore volume below 0.54 μm of fine pore is relative to thin below 1.1 μm of the fine pore The ratio of pore volume is more than 80%.When pore volume below 1.1 μm of fine pore is more than 0.100mL/g, when making negative pole Binding material is penetrated into the pore, and stripping electrode intensity decreases, cycle characteristics may reduce.In addition, 0.54 μm of fine pore with Under pore volume when being less than 80% relative to the ratio of the pore volume below 1.1 μm of the fine pore, it is viscous when making negative pole Knot material still can be penetrated into the pore, cannot get sufficient stripping electrode intensity, cycle characteristics may reduce.
Pore below 1.1 μm of the fine pore using mercury injection apparatus measure of carbonaceous coated graphite plasmid of the present invention holds Product is preferably below 0.090mL/g, more preferably below 0.085mL/g.
Pore volume below 0.54 μm of the fine pore of carbonaceous coated graphite plasmid of the present invention is held relative to the pore The ratio of product (pore volume below 1.1 μm of fine pore) is preferably more than 81%, and more preferably more than 82%.
In addition, dibutyl phthalate (DBP) oil absorption of the carbonaceous coated graphite particle of the present invention is 40.0mL/ Below 100g.During more than the numerical value, binding material when making negative pole is penetrated into the pore, stripping electrode intensity decreases, is followed Ring property may reduce.
In addition, dibutyl phthalate (DBP) oil absorption of the graphite particle of the present invention is preferably 38.0mL/100g Hereinafter, more preferably below 37.0mL/100g.
Average grain diameter as the carbonaceous coated graphite particle of end article is preferably 1~50 μm of scope, further excellent Elect 5~30 μm of scope as.The specific surface area determined by BET method is preferably 6.0m2/ below g, more preferably 4.0m2/g Below.
In addition, the 1360cm that the Raman spectroscopy by using argon laser of above-mentioned carbonaceous coated graphite particle determines-1Peak Intensity (I1360) and 1580cm-1Peak intensity (I1580) the ratio between I1360/I1580(R values) be more than graphite R values, preferably 0.05~ 0.80。
3. the manufacture method of carbonaceous coated graphite particle
[pressurization operation]
The manufacture method of carbonaceous coated graphite particle of the present invention does not limit, preferably first to above-mentioned spherical and/or Ellipsoid shaped graphite carries out anisotropic pressurized treatments.Anisotropic pressurized treatments, which refer to apply along specific direction, presses Power, it is not isotropic pressurization.Isotropic pressurization is, for example, to carry out isotropism using pressure mediums such as gas, liquid The method of pressurization, in comparative example 2,3 described later, use isostatic cool pressing.
Anisotropic pressurization is preferably the pressurization carried out from a direction or both direction.The side of anisotropic pressurization Method is not particularly limited, and can enumerate such as molding, roll squeezer, extrusion molding, generally be carried out in normal temperature, air.Pressurization Power, anisotropic direction do not limit, preferably with carbonaceous coated graphite particle is used for into lithium ion secondary battery negative pole material Plus-pressure, the anisotropic compression aspect of negative pole formation process during material suitable degree is carried out.On plus-pressure, such as It is 2000~3000cm in internal volume3Mould in be highly filled with 5~10cm, added with 40~300MPa pressure Pressure.
When situation of adhesion etc. is produced in pressurized treatments, broken process can be imported after pressurized treatments as needed. In pressurized treatments, carbonaceous precursor material, organic material, the nothings such as fiber, the noncrystalline hard carbon of carbonaceous or graphite can be added Machine material, metal material, it can not also add.In the case of addition, the combination in compression aspect and non-pressurised direction becomes multiple Miscellaneous, therefore, pressurization result is closer to isotropic pressurization.In the case where not adding, pressurization result becomes simpler, adds Pressure direction increases compared with the situation of other materials is added when the difference of the orientation in non-pressurised direction is with pressurized treatments.
[mixed processes]
Resulting pressurized treatments thing is mixed with carbonaceous precursor.As long as mixed processes can carry out homogeneous, mixing does not have then It is particularly limited to, known mixed method can be used.It is preferred that by the graphite particle of solid with solid or semisolid (comprising sticky Liquid) carbonaceous precursor mixing.Mink cell focus is solid at normal temperatures.
In the case where the carbonaceous precursor of the liquid such as oil in tar light oil, tar is mixed as solvent, preferably exist Solvent volatilization is set to carry out ensuing calcination process again at less than about 200 DEG C of temperature in advance.On blending ratio, so that carbonaceous Material is in a manner of the ratiometer of end article reaches the scope of 0.1~3.0 mass parts relative to the mass parts of graphite particle 100 Raw material is mixed.Mixing can also be carried out together with the heating process described later for heating process.Heat the side of mixing Method is not particularly limited, and can illustrate double-screw type kneader with heating arrangements such as heater, thermal mediums etc..At mixing During reason, carbonaceous precursor material, organic material, inorganic material, the gold such as fiber, the noncrystalline hard carbon of carbonaceous or graphite can be added Belong to material.Mixed processes can also be calcined upon mixing with the calcination process recorded below while carrying out.
[calcination process]
Resulting mixture is calcined at 700~2200 DEG C.The method of calcination processing is not particularly limited, excellent Calcined while being selected in stirring, the calcining of homogeneous can be carried out using the method for rotary kiln, therefore preferably.On calcining temperature Degree, as long as the temperature eventually arrived at is within the above range, then can be heat-treated in multiple stages.Atmosphere can be oxidation Property or it is non-oxidizable in any one, can stage by stage using both.Non-oxidizing atmosphere can illustrate argon gas, helium, nitrogen Gas etc..Calcination time is preferably 5 minutes~30 hours.In addition, as Temperature Distribution when heating up and when calcining, line can be used Property heating, the at certain intervals various forms such as interim heating of keeping temperature.
The manufacture method of the carbonaceous coated graphite particle of the present invention does not preferably include pulverizing process after firing.In addition, can To make attachment, embedded, compound rear use between different types of graphite material before calcination processing.Carbonaceous or stone can also be made It is the carbonaceous precursor materials such as the fiber of black matter, noncrystalline hard carbon, organic material, inorganic material, metal material attachment, embedded, compound Used after on the graphite particle of core.
4. negative pole
In addition, the present invention is the lithium ion secondary battery cathode containing above-mentioned carbonaceous coated graphite particle, in addition for Use the lithium rechargeable battery of the negative pole.
The negative pole of the lithium rechargeable battery of the present invention makes according to the manufacturing process of common negative pole, as long as energy The method for accessing the negative pole chemically, in electrochemistry stably does not have any restrictions then.In the making of negative pole, it is preferably used in Bonding agent and previously prepared cathode agent are added in the carbonaceous coated graphite particle of the present invention.It is preferably pair as bonding agent The electrolyte material with exhibit stabilization in electrochemistry in chemistry, can use such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride Deng the toners such as fluorine resin powder, polyethylene, polyvinyl alcohol, carboxymethyl cellulose etc..They can also be applied in combination. Bonding agent is generally used with the mass % of about 1 mass % in the total amount (drying schedule) of cathode agent~about 20 ratio.Therefore, The carbonaceous coated graphite particle of the present invention is generally used with 99~80 mass % ratio (drying schedule).
More specifically, the negative material of the present invention is adjusted to desired granularity using classification etc. first, with bonding agent Mixing, makes resulting mixture be scattered in solvent and form pasty state, prepares cathode agent.That is, by the negative pole material of the present invention Material and bonding agent are mixed with water, isopropanol, N- methyl pyrrolidones, dimethylformamide equal solvent, and resulting slurry is made Mixing is stirred with known mixer, mixer, kneading machine, kneader etc., prepares paste.The paste is applied to current-collecting member One or two sides on and dry, obtain being adhesive with the negative pole of anode mixture layer uniformly and securely.The thickness of anode mixture layer For 10~200 μm, preferably 20~100 μm.
The negative pole manufactured by the cathode agent of the carbonaceous coated graphite particle containing the present invention is with the state quilt of graphite particle Anisotropically pressurizeed, therefore, after anode mixture layer is formed, without compressing when negative pole is made In the case of, it can also make electrode density higher.
In addition, the negative pole of the present invention can also be by by the negative material of the present invention and the resin such as polyethylene, polyvinyl alcohol Powder carries out dry type mixing and hot forming is carried out in mould to make.
When carrying out suppressing the crimping such as pressurization after forming anode mixture layer, anode mixture layer and current collection can be further improved The adhesive strength of body.
Shape as the collector used in the making of negative pole is not particularly limited, preferably foil-like, grid, metal lath (エ キ ス パ Application De メ タ Le) etc. is netted etc..As the material of collector, preferably copper, stainless steel, nickel etc..In the situation of foil-like Under, the thickness of collector is preferably from about 5 μm~about 20 μm.
It should be noted that in the range of the purpose of the present invention is not damaged, negative pole of the invention can mix, interior bag, Coat or be laminated with carbonaceous material, organic matter, metal, the metallic compounds such as different types of graphite material, noncrystalline hard carbon Deng.
The negative pole manufactured by the cathode agent of the carbonaceous coated graphite particle containing the present invention is with the state quilt of graphite particle Anisotropically pressurizeed, therefore, after anode mixture layer is formed, caused by compacting pressurization when can suppress to make negative pole The deformation of particle and the damage of the clad associated with this, even if electrode density is high density, be also able to maintain that high first Efficiency for charge-discharge, high speed charge-discharge characteristic and cycle characteristics.
[positive pole]
The positive pole used in the lithium secondary battery of the present invention positive electrode, bonding agent and conductive agent by that for example will be made up of Anode mixture be applied on the surface of collector to be formed.The material (positive active material) of positive pole, which preferably selects, to be absorbed/ The material of an adequate amount of lithium is desorbed, is that lithium-containing transition metal oxide, transition metal chalcogenide, barium oxide and its lithiumation are closed The lithium-containing compounds such as thing, formula MXMo6S8-Y(in formula, M is at least one transition metal, and X is the number of the scope of 0≤X≤4 Value, Y are the numerical value of the scope of 0≤Y≤1) represented by thank freire (Chevrel) phase compound, activated carbon, activated carbon fine Dimension etc..
Barium oxide is V2O5、V6O13、V2O4、V3O8Represented barium oxide.
Lithium-containing transition metal oxide is the composite oxides of lithium and transition metal, can be dissolved lithium and two or more Transition metal.Composite oxides may be used alone, can also be used in combination two or more.
Specifically, lithium-containing transition metal oxide is by LiM1 1-XM2 XO2(in formula, M1、M2For at least one transition metal member Element, X are the numerical value of the scope of 0≤X≤1) or LiM1 1-YM2 YO4(in formula, M1、M2For at least one transition metal, Y 0 The numerical value of the scope of≤Y≤1) represent.
By M1、M2The transition metal of expression is Co, Ni, Mn, Cr, Ti, V, Fe, Zn, Al, In, Sn etc., is preferably Co, Fe, Mn, Ti, Cr, V, Al etc..Preferable concrete example is LiCoO2、LiNiO2、LiMnO2、LiNi0.9Co0.1O2、 LiNi0.5Co0.5O2Deng.
Lithium-containing transition metal oxide can for example obtain by the following method：With lithium, the oxide of transition metal, hydrogen-oxygen Compound, salt etc. are used as initiation material, these initiation materials are mixed according to the composition of desired metal oxide, in oxygen Calcined under atmosphere at a temperature of 600~1000 DEG C.
Positive active material can be used alone above-claimed cpd, can also be applied in combination two or more.For example, can be The carbon salt such as lithium carbonate are added in positive pole.In addition, when forming positive pole, known conductive agent, bonding can be suitably used The various additives such as agent.
[manufacture of positive pole]
Positive pole above-mentioned positive electrode, bonding agent and the conductive agent for assigning electric conductivity to positive pole by will be made up of just Pole mixture is applied on the two sides of collector and forms positive electrode material mixture layer to make.As bonding agent, can use and negative pole The bonding agent identical material used in making.As conductive agent, conductive agent known to graphite compound, carbon black etc. can be used.
The shape of collector is not particularly limited, foil-like or grid, metal lath etc. can be used netted etc..Collector Material is aluminium, stainless steel, nickel etc..Its thickness is preferably 10~40 μm.
Positive pole also with negative pole likewise it is possible to make anode mixture be scattered in solvent and form pasty state, by the pasty state just Pole mixture is applied on collector and dries and form positive electrode material mixture layer, can also further be carried out after positive electrode material mixture layer is formed The crimping such as compacting pressurization.Thus, make positive electrode material mixture layer uniform and gluing on current-collecting member securely.
[nonaqueous electrolyte]
The nonaqueous electrolyte used in lithium rechargeable battery as the present invention, it can use and be used as common non-water power Electrolytic salt, the LiPF used in solution liquid6、LiBF4、LiAsF6、 LiClO4、LiB(C6H5)、LiCl、LiBr、LiCF3SO3、 LiCH3SO3、LiN(CF3SO2)2、 LiC(CF3SO2)3、LiN(CF3CH2OSO2)2、LiN(CF3CF2OSO2)2、 LiN (HCF2CF2CH2OSO2)2、LiN((CF3)2CHOSO2)2、LiB[{C6H3(CF3)2}]4、 LiAlCl4、LiSiF6Deng lithium salts.From oxygen From the viewpoint of changing stability, particularly preferred LiPF6、 LiBF4。
Electrolytic salinity in electrolyte is preferably 0.1~5.0mol/L, more preferably 0.5~3.0mol/L.
Nonaqueous electrolyte can be the nonaqueous electrolyte of liquid, or the high score such as solid electrolyte or gel electrolyte Sub- electrolyte.In the former case, nonaqueous electrolyte battery is configured to so-called lithium rechargeable battery, in the feelings of the latter Under condition, nonaqueous electrolyte battery is configured to the macromolecules such as polymer solid electrolyte battery, polymer gel electrolyte battery Electrolytic cell.
As the solvent for preparing nonaqueous electrolyte liquid, ethylene carbonate, propylene carbonate, carbonic acid diformazan can be used The carbonic esters such as ester, diethyl carbonate, 1,1- dimethoxy-ethanes or 1,2- dimethoxy-ethanes, 1,2- diethoxyethane, four Hydrogen furans, 2- methyltetrahydrofurans, gamma-butyrolacton, 1,3- dioxolanes, the ring of 4- methyl-1,3-dioxies penta, methyl phenyl ethers anisole, ether Deng nitrile, trimethylborate, silicic acid such as the thioethers such as ether, sulfolane, methyl sulfolane, acetonitrile, chlorine nitrile (Network ロ ロ ニ ト リ Le), propionitrile Four methyl esters, nitromethane, dimethylformamide, 1-METHYLPYRROLIDONE, ethyl acetate, trimethyl orthoformate, nitrobenzene, benzene first Acyl chlorides, benzoyl bromide, thiophane, dimethyl sulfoxide (DMSO), 3- methyl -2-The non-matter such as oxazolidone, ethylene glycol, dimethyl sulfite Sub- property organic solvent etc..
In general, under the looking at using graphite cathode material, electrolyte uses the body without propylene carbonate (PC) System.PC easily decomposes reaction in graphite surface, inner pressure of battery is increased because gas produces, in addition, on negative material A large amount of generation cleavage reaction products (SEI overlay films), therefore battery behavior is reduced, therefore it is not preferred.The carbonaceous cladding of the present invention In graphite particle, spherical and/or ellipsoid shaped graphite is anisotropically pressurizeed and has further carried out carbonaceous cladding, therefore, Carbonaceous coated graphite particle surface and propylene carbonate it is reactive low, even if containing propylene carbonate in the electrolytic solution, be used for The battery behavior during negative material of lithium rechargeable battery is also in no way inferior.
Make feelings of the nonaqueous electrolyte for polyelectrolytes such as polymer solid electrolyte or polymer gel electrolytes Under condition, preferably use by the use of the macromolecule after plasticizer (nonaqueous electrolytic solution) gelation and be used as matrix.As the above-mentioned matrix of composition Macromolecule, particularly preferably using ether system high-molecular compound, the polymethacrylates system such as PEO and its crosslinked High-molecular compound, polyacrylate system high-molecular compound, polyvinylidene fluoride or vinylidene difluoride-hexafluoropropylene copolymer Etc. fluorine system high-molecular compound etc..
It can coordinate plasticizer in above-mentioned polymer solid electrolyte or polymer gel electrolyte, can as the plasticizer To use above-mentioned electrolytic salt, nonaqueous solvents.In the case of polymer gel electrolyte, the non-aqueous solution electrolysis as plasticizer Electrolytic salinity in liquid is preferably 0.1~5.0mol/L, more preferably 0.5~2.0mol/L.
The preparation method of polymer solid electrolyte is not particularly limited, and can enumerate for example：The high score of matrix will be formed The method that sub- compound, lithium salts and nonaqueous solvents (plasticizer) are mixed and heated and melt high-molecular compound；Make macromolecule After compound, lithium salts and nonaqueous solvents (plasticizer) are dissolved in organic solvent, make the method for mixing organic solvent evaporation； Polymerizable monomer, lithium salts and nonaqueous solvents (plasticizer) are mixed, ultraviolet, electron ray, molecular beam etc. are irradiated to mixture, Method for polymerizeing polymerizable monomer and obtaining polymer etc..
Here, the ratio of the nonaqueous solvents (plasticizer) in above-mentioned solid electrolyte is preferably 10~90 mass %, it is more excellent Elect 30~80 mass % as.During less than 10 mass %, electrical conductivity reduces, and during more than 90 mass %, mechanical strength weakens, it is difficult to enters Row film forming.
[dividing plate]
In the lithium rechargeable battery of the present invention, dividing plate can also be used.The material of dividing plate is not particularly limited, can be with Enumerate such as weaving cotton cloth, non-woven fabrics, synthetic resin microporous film.As the material of aforementioned barriers, preferably synthetic resin-made Micro-porous film, wherein, from the aspect of thickness, film-strength, film resistance, preferred polyolefm system micro-porous film.Specifically, it is excellent Elect polyethylene and polypropylene microporous film or the micro-porous film that they are combined etc. as.
[manufacture of lithium rechargeable battery]
The lithium rechargeable battery of the present invention is by the way that the negative pole, positive pole and nonaqueous electrolyte of above-mentioned composition are for example born Pole, nonaqueous electrolyte, the order of positive pole are laminated and housed in the exterior material of battery to form.Furthermore, it is possible to negative Pole and the outside of positive pole configuration nonaqueous electrolyte.
In addition, the structure of the lithium rechargeable battery of the present invention is not particularly limited, for its shape, form also without spy Do not limit, can be according to purposes, carrying equipment, required charge/discharge capacity etc., from cylinder type, square, Coin shape, button type Arbitrarily selected in.In order to obtain the higher hermetic type battery with nonaqueous electrolyte of security, preferably using possessing in overcharge etc. Inner pressure of battery rise is perceived when abnormal and blocks the structure of the means of electric current.
In the case where lithium rechargeable battery is polymer solid electrolyte battery, polymer gel electrolyte battery, The structure being sealing into laminated film can also be made.
Embodiment
Then, the present invention is more specifically illustrated by embodiment, but the invention is not restricted to these embodiments.Separately Outside, in following embodiment and comparative example, it is attached with the present invention's by the part at least surface as shown in figure 1, making Collector (negative pole) 7b of cathode agent 2 and the coin shape for the monopole evaluation formed to electrode (positive pole) 4 being made up of lithium paper tinsel Secondary cell is evaluated.Actual battery can be made based on method known to idea of the invention foundation.
Each physical property of this specification is measured by following method.
1) average grain diameter (μm)：The cumulative frequency of the size distribution determined using laser diffraction formula particle size distribution meter is with volume Percentage reaches 50% particle diameter.
2) ratio (%) of carbonaceous：Raw material (including a variety of situations) simple substance of carbonaceous precursor is assigned and carbonaceous cladding stone Black particle identical thermal history, the carbide of carbonaceous simple substance is prepared, obtain the Residual carbon of raw material.Carried out by resulting Residual carbon Conversion, calculate carbonaceous ratio shared in carbonaceous coated graphite particle.
3) pore volume (mL/g)：It is measured using mercury injection method, obtains the relation of fine pore and pore volume, is calculated thin Below 1.1 μm of aperture and less than 0.54 μm of total pore volume.
4) DBP oil absorptions (mL/100g)：According to JIS K6217, input 40g measure materials, are 4mL/ points in rate of addition Clock, rotating speed implement measure under conditions of being 125rpm, untill the maximum of moment of torsion is confirmed.Shown since the measure In the range of during peak torque, it is every to would indicate that dropwise addition oil mass during 70% moment of torsion of peak torque is scaled material 100g, calculate DBP oil absorptions.
(embodiment 1)
[making as the carbonaceous coated graphite particle of negative material]
The spherical native graphite particle for being processed into 15 μm of average grain diameter is each to different with 50MPa progress using moulding press Property pressurization.It is carried out after crushing in a manner of average grain diameter is reached 15 μm, relative to 100 mass parts, so that solid constituent The mode that ratio reaches 2.0 mass parts adds oil solution in the tar of coal tar asphalt (Residual carbon 50%), is mediated in twin-screw 150 DEG C are heated in machine, is mixed 60 minutes.Resulting mixture is circulated the bar of nitrogen using tube furnace with 2L/ minutes 1300 DEG C, the heat treatment of 3 hours are carried out under part, thus obtains end article.
[making of cathode agent paste]
Using 98 mass parts of above-mentioned negative material, the mass parts of carboxymethyl cellulose 1 and styrene-fourth two as bonding agent The mass parts of alkene rubber 1 are added to the water, stirring, prepare cathode agent paste.
[making of working electrode (negative pole)]
Above-mentioned cathode agent is pasted and is applied to equably thickness on copper foil, solvent is volatilized in a vacuum, at 90 DEG C, is done It is dry, anode mixture layer is pressurizeed using roll squeezer, electrode density is adjusted to 1.70g/cm3.By copper foil and cathode agent Layer is punched into the cylindric of diameter 15.5mm, makes the work being made up of collector and the cathode agent being sealed on the collector Electrode (negative pole).
[making to electrode (positive pole)]
Lithium metal foil is pressed on nickel screen, is punched into diameter 15.5mm toroidal, makes and includes what is be made up of nickel screen Collector and the lithium metal foil (thickness 0.5mm) that is sealed on the collector to electrode.
[electrolyte, dividing plate]
Make LiPF6The volume % of 33 volume %- methyl ethyl carbonates of ethylene carbonate 67 is dissolved in reach 1mol/L concentration In the mixed solvent, prepare nonaqueous electrolytic solution.The nonaqueous electrolytic solution for making to obtain is infiltrated in polypropylene porous plastid (20 μm of thickness) In, make the dividing plate for being impregnated with electrolyte.
[making of evaluation battery]
The coin shape secondary cell shown in Fig. 1 is made as evaluation battery.
In exterior cup 1 and outer tinning 3, in its periphery sandwiched insulation air cushion 6, two peripheries are riveted closed.Evaluation electricity Pond is to be sequentially laminated with the collector 7a being made up of nickel screen, the circle being made up of lithium paper tinsel from the inner surface of outer tinning 3 inside it Tubular to electrode (positive pole) 4, be impregnated with dividing plate 5, the collector being made up of the copper foil for being attached with cathode agent 2 of electrolyte (negative pole) 7b battery system.
Above-mentioned evaluation battery makes as follows：The dividing plate 5 for being impregnated with electrolyte is clamped to collector 7b and is sealed at current collection Body 7a between electrode 4 and after being laminated, collector 7b being housed in exterior cup 1, electrode 4 will be housed in outer tinning 3, Exterior cup 1 and outer tinning 3 are combined, will further in exterior cup 1 and the periphery sandwiched of outer tinning 3 insulation air cushion 6 The riveting of two peripheries is closed.Charge-discharge characteristic is determined by following method.Show the result in table 1.
[charge and discharge electric test]
0.9mA constant current charge is carried out, untill circuit voltage reaches 1mV, then, reaches 1mV in circuit voltage At the time of switch to constant voltage to charge, and then, the turn on angle during reaching 20 μ A by current value obtains charging capacity (unit： mAh/g).Then, 10 minutes are suspended.Then, constant current discharge is carried out with 0.9mA current value, until circuit voltage reaches Untill 1.5V, discharge capacity (unit is obtained by the turn on angle of this period：mAh/g).As the 1st circulation.Then, will Charging current is set as 1C, discharge current is set as into 2C, and discharge and recharge is carried out in the same manner as the 1st circulation.1C, 2C electric current Value is calculated by the discharge capacity of the 1st circulation and the active material weight of negative pole.
First efficiency for charge-discharge is calculated by following formula (1).
First efficiency for charge-discharge (%)=100 × ((discharge capacity of 1 circulation of charging capacity-the of the 1st circulation)/ The discharge capacity of 1st circulation) ... (1)
In addition, 1C charge rates are calculated by following formula (2).
1C charge rates (%)=100 × (electric discharge of the charging capacity/1st time circulation of the CC parts in 1C current values is held Amount) ... (2)
In addition, 2C discharge rates are calculated by following formula (3).
2C discharge rates (%)=100 × (discharge capacity of the discharge capacity/1st time circulation in 2C current values) ... (3)
In addition, cycle characteristics is measured in the following manner.Constant current charge is carried out with 1C current values, until circuit voltage Untill reaching 1mV, then, switch to constant voltage to charge, persistently charge to untill current value reaches 20 μ A, then suspend 10 points Clock.Then, constant current discharge is carried out with 2C current value, untill circuit voltage reaches 1.5V.The discharge and recharge is repeated Row 50 times, cycle characteristics is calculated using following formula (4) by resulting discharge capacity.
Cycle characteristics (%)=100 × (discharge capacity of the discharge capacity/1st time circulation of the 50th circulation) ... (4)
It should be noted that in this experiment, lithium ion is absorbed into the process in negative material as charging, by lithium ion Electric discharge is used as from the process of negative material desorption.
(embodiment 2)
In embodiment 1, it is 1.75g/cm to make electrode density during Cell Performance Evaluation3, in addition, with embodiment 1 Similarly evaluated.Evaluation result is shown in Table 1.
(embodiment 3)
In embodiment 1, carbonaceous covering amount is changed to the amount shown in table 1, in addition, made similarly to Example 1 Carbonaceous coated graphite particle is made, evaluation battery is made similarly to Example 1 and is evaluated.
(embodiment 4)
In embodiment 1, pressure during pressurized treatments is set as 100MPa, in addition, made similarly to Example 1 Carbonaceous coated graphite particle is made, it is 1.70g/cm to make electrode density3To be evaluated.Evaluation result is shown in Table 1.
(embodiment 5)
In embodiment 1, pressure during pressurized treatments is set as 150MPa, in addition, made similarly to Example 1 Carbonaceous coated graphite particle is made, it is 1.70g/cm to make electrode density3To be evaluated.Evaluation result is shown in Table 1.
(embodiment 6)
In embodiment 1, carbonaceous covering amount is changed to the amount shown in table 1, in addition, entered similarly to Example 1 Row evaluation.Evaluation result is shown in Table 1.
(comparative example 1)
In embodiment 1, without pressurized treatments, in addition, carbonaceous coated graphite grain is manufactured similarly to Example 1 Son, evaluation battery is made similarly to Example 1 and is evaluated.
(comparative example 2)
In embodiment 1, the method for pressurized treatments is set as isostatic cool pressing, isotropically pressurize 50MPa, except this with Outside, coated natural graphite material is manufactured similarly to Example 1, is made evaluation battery similarly to Example 1 and is evaluated.
(comparative example 3)
In comparative example 2, electrode density during Cell Performance Evaluation is set as 1.75g/cm3, in addition, compared with Example 2 is similarly evaluated.Evaluation result is shown in Table 1.
(comparative example 4)
In embodiment 1, carbonaceous covering amount is changed to the amount shown in table 1, in addition, made similarly to Example 1 Carbonaceous coated graphite particle is made, evaluation battery is made similarly to Example 1 and is evaluated.
(comparative example 5)
In embodiment 1, carbonaceous covering amount is changed to the amount shown in table 1, in addition, made similarly to Example 1 Carbonaceous coated graphite particle is made, evaluation battery is made similarly to Example 1 and is evaluated.
(comparative example 6)
In embodiment 1, pressure during pressurized treatments is set as 10MPa, in addition, entered similarly to Example 1 Row evaluation.Evaluation result is shown in Table 1.
(comparative example 7)
In embodiment 1, pressure during pressurized treatments is set as 10MPa, carbonaceous covering amount is set as 3.0 mass Part, in addition, evaluated similarly to Example 1.Evaluation result is shown in Table 1.
(comparative example 8)
In embodiment 1, pressure during pressurized treatments is set as 30MPa, carbonaceous covering amount is set as 3.0 mass Part, in addition, evaluated similarly to Example 1.Evaluation result is shown in Table 1.
(comparative example 9)
In embodiment 1, pressure during pressurized treatments is set as 10MPa, carbonaceous covering amount is set as 0.15 mass Part, in addition, evaluated similarly to Example 1.Evaluation result is shown in Table 1.
The graphite particle for carrying out anisotropy pressurization and being formed meets in the embodiment 1~6 of following (1)~(3), discharges Capacity, first efficiency for charge-discharge, high speed charge-discharge characteristic and cycle characteristics are good.From the comparison of embodiment 1,2, even if entering One step improves electrode density, can also maintain the characteristic.
(1) content of carbonaceous material is formed relative to the carry out anisotropy pressurization in carbonaceous coated graphite plasmid The mass parts of graphite particle 100 are 0.1~3.0 mass parts.
(2) it is below 0.100mL/g using the pore volume below 1.1 μm of the fine pore of mercury injection apparatus measure, and pore Pore volume below 0.54 μm of footpath is more than 80% relative to the ratio of the pore volume.
(3) dibutyl phthalate (DBP) oil absorption is below 40.0mL/100g.
On the other hand, graphite particle not by the comparative example 1 of carry out pressurized treatments, carried out isotropism pressurized treatments Comparative example 2,3, comparative example 4 of the covering amount less than 0.1%, comparative example of the covering amount more than 3% of carbonaceous material of carbonaceous material 5th, the pore volume below 1.1 μm of fine pore is thin relative to this more than the pore volume below 0.100mL/g, 0.54 μm of fine pore The ratio of pore volume is less than thin below comparative example 6 of the 80% and DBP oil absorptions more than 40.0mL/100g, 1.1 μm of fine pore Pore volume more than the pore volume below 0.1mL/g comparative example 7,0.54 μm of fine pore relative to 1.1 μm of fine pore below Comparative example 8 of the ratio of pore volume less than 80%, the pore volume below 1.1 μm of fine pore are inhaled more than 0.100mL/g and DBP In comparative example 9 of the oil mass more than 40.0mL/100g, high discharge capacity, high first efficiency for charge-discharge, height can not be reached simultaneously High speed charge-discharge characteristic and excellent cycle characteristics.On having carried out the comparative example 2,3 of isotropism pressurized treatments, entering one In the case that step improves electrode density, the reduction of first efficiency for charge-discharge, high speed charge-discharge characteristic and cycle characteristics is confirmed.
Industrial applicability
The negative material of carbonaceous coated graphite plasmid comprising the present invention is as ion secondary battery cathode material lithium Negative material with good discharge capacity, first efficiency for charge-discharge, high speed charge-discharge characteristic and cycle characteristics.It can play Its characteristic and be used for the negative pole of small-sized to large-scale high performance lithium rechargeable battery.
Symbol description
1 exterior cup
2 cathode agents
3 outer tinnings
4 pairs of electrodes
5 are impregnated with the dividing plate of electrolyte solution
6 insulation air cushions
7a, 7b collector
10 aluminium sheets
12 two-sided tapes
15 negative materials
17 directions of arrow.

Claims (3)

1. a kind of ion secondary battery cathode material lithium graphite particle, it is to enter to spherical and/or ellipsoid shaped graphite At least a portion on the surface for the graphite particle that row anisotropy is pressurizeed and formed has the carbonaceous coated graphite of carbonaceous material Plasmid, the carbonaceous coated graphite plasmid overabundance of amniotic fluid foot state (1)~(3),
(1) content of the carbonaceous material relative to the carry out anisotropy pressurization in carbonaceous coated graphite plasmid and The mass parts of graphite particle 100 of formation are 0.1~3.0 mass parts；
(2) it is below 0.100mL/g using the pore volume below 1.1 μm of the fine pore of mercury injection apparatus measure, and fine pore Less than 0.54 μm of pore volume is more than 80% relative to the ratio of the pore volume below 1.1 μm of the fine pore；
(3) dibutyl phthalate (DBP) oil absorption is below 40.0mL/100g.
2. a kind of lithium ion secondary battery negative pole, it contains the ion secondary battery cathode material lithium stone described in claim 1 Black plasmid.
3. a kind of lithium rechargeable battery, it has the lithium ion secondary battery negative pole described in claim 2.
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