CN103190018B - Lithium ion battery, and battery module utilizing same - Google Patents

Lithium ion battery, and battery module utilizing same Download PDF

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Publication number
CN103190018B
CN103190018B CN201180045723.8A CN201180045723A CN103190018B CN 103190018 B CN103190018 B CN 103190018B CN 201180045723 A CN201180045723 A CN 201180045723A CN 103190018 B CN103190018 B CN 103190018B
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Prior art keywords
lithium ion
active material
negative electrode
carbon
electrode active
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CN201180045723.8A
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CN103190018A (en
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西村悦子
田中明秀
冯孝亮
本棒英利
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Resonac Corp
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Hitachi Chemical 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
    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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

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

Abstract

The present invention provides: a lithium ion battery which comprises a negative electrode that contains a negative electrode active material capable of absorbing and desorbing lithium, a positive electrode, a nonaqueous electrolyte and a nonaqueous solvent; a battery module which uses the lithium ion battery; and a power storage system for a mobile body and a stationary power storage system. The negative electrode active material is composed of composite carbon particles, each of which has a coating layer of low crystallinity carbon on the surface of a graphite nucleus material. The coating layer has functional groups, namely C=O groups, C-OH groups and C-O groups on the surface, and the ratio of oxygen atoms in the total of carbon atoms and oxygen atoms contained in the coating layer is from 2 atom% to 5 atom%. The negative electrode active material has at least one peak respectively in a temperature range not less than 350 DEG C but less than 600 DEG C and in a temperature range from 600 DEG C to 850 DEG C (inclusive) as determined by thermogravimetric measurement, and the peak temperature difference between an oxidation peak that has the highest peak temperature within the temperature range from 350 DEG C to 850 DEG C (inclusive) and an oxidation peak that has the lowest peak temperature within the temperature range from 350 DEG C to 850 DEG C (inclusive) is 300 DEG C or less.

Description

Lithium ion battery and the battery module using this battery
Technical field
The present invention relates to a kind of lithium ion battery and the battery module using this battery.
Background technology
Lithium ion battery has a high-energy-density, therefore as electric automobile, the battery of electric power storage and receive publicity. Particularly electric automobile, including not carrying the zero-emission electric automobile of engine, be equipped with the mixed of both engine and secondary cell Close power electric automobile and the plug-in hybrid electric automobile directly being charged by system power supply.In the present invention, electronic Automobile refers to above-mentioned various automobile.Additionally, be desirable to it as storage electric power, and the unusual time being cut off in power system The purposes of the stationary electric power stocking system of supply electric power.
For such multiple use, lithium ion battery requires there is excellent durability.Even if that is, environment temperature Degree uprises, and the rate of descent being capable of the capacity of charging and discharging is also little, and through for a long time, battery capacity sustainment rate is also high.Especially It is lithium ion battery used for electric vehicle, be exposed to 40 DEG C～70 because of the radiant heat from road surface or from in-car heat transfer DEG C hot environment, long-term preservation characteristics under these circumstances and the raising of cycle life become an important exploitation class Topic.
As for suppressing the prior art that capacity during High temperature storage declines or circulation deteriorates, studying high durable The various technology such as electrode material or electrolyte.Particularly negative pole, along with the decomposition reaction of electrolyte, the lithium quilt that negative pole is adsorbed Consume, lead to the capacity of battery to decline.In order to suppress this side reaction, disclose multiple sides of the modifying surface to negative pole Method.
Japanese Unexamined Patent Publication 6-168725 publication discloses a kind of invention about battery, and this battery employs 2000 Under high temperature more than DEG C, carbonizable substance is processed and made after its graphitization, pulverized, then the heat treatment institute applying more than 2000 DEG C Negative pole, Japanese Unexamined Patent Publication 2000-156230 publication discloses a kind of negative electrode active material, and it is by will use amorphous carbon The offspring that the primary particle of coated graphite surface gained carries out pelletize and formed is constituted.
Japanese Unexamined Patent Publication 2002-134171 publication discloses a kind of invention about battery, and this battery is in negative electrode active material Employ in matter by the carbon of water-soluble high-molecular substance clad surface electronegative in water, Japanese Unexamined Patent Publication 5-275077 Publication discloses the invention being coated with carbon surface with the solid electrolyte film of lithium-ion-conducting.
After Japanese Unexamined Patent Publication 2000-264614 publication discloses one kind surfactant process graphite particle, in graphite The invention of the clad being made up of carbon is formed on the surface of particle, Japanese Unexamined Patent Publication 2001-229914 publication discloses one kind and exists Graphite surface forms amorphous carbon film layer, the invention of suppression electrolyte decomposition.
Japanese Unexamined Patent Publication 2006-24374 publication discloses one kind in crystallinity carbon particle（Primary particle）Surface on Form carbon coating layer, and make primary particle combine the related invention of the carbon offspring of gained by this carbon coating layer, Japan is special Open 2006-228505 publication and disclose a kind of invention about negative pole graphite, this negative pole graphite is characterised by, put down All particle diameter is 5 μm～50 μm, and true specific gravity is 2.20g/cm3More than, it is 8m by the specific surface area of nitrogen adsorption gained2/ below g, by The specific surface area of carbon dioxide adsorption gained is 1m2/ below g, the oxygen atom being measured by x-ray photoelectron spectrophotometric spectra is dense Spend for more than 0.7atom%.
Japanese Unexamined Patent Publication 2007-42571 publication is the invention about material with carbon element, and described material with carbon element is surveyed by X-ray diffraction The face interval d002 in fixed calculated carbon 002 face is 0.340nm～0.390nm, and special provision He true density and CO2Inhale Attached amount.
Japanese Unexamined Patent Publication 2009-187924 publication discloses a kind of crystallite dimension obtaining by X-ray diffraction method analysis Lc is 20nm～90nm, and the face interval d002 in carbon 002 face is 0.3354nm～0.3370nm, and defines low knot from the teeth outwards The related invention of the negative material of crystalline substance carbon.
Content of the invention
Problems to be solved by the invention
The lithium ion battery that used for electric vehicle or electric power stores, is positioned over hot environment sometimes in the charge state In, thus battery capacity can be led to decline because of self discharge.It is an object of the invention to the self discharge that suppression is led to because of negative pole, real The long lifetime of existing lithium ion battery.
The method of solve problem
The present inventor etc. have carried out positive research to solve the above problems, even if it is found that in high temperature environments After lithium ion battery discharge and recharge or placing, the method that battery capacity is not easy to decline.
According to the 1st mode of the present invention, provide a kind of lithium ion battery, it contains and comprises to adsorb and release lithium The negative pole of negative electrode active material, positive pole, nonaqueous electrolyte and nonaqueous solvent, negative electrode active material is in graphite particle（Stone Black nuclear material）Surface on have low-crystalline carbon clad compound carbon particle, aforementioned clad has C=O, C-OH With C-O functional group, the oxygen atom containing ratio in the carbon atom of aforementioned clad and the total amount of oxygen atom be 2atom%～ 5atom%, in aerial thermogravimetric algoscopy, negative electrode active material at least respectively at 350 DEG C more but less than 600 DEG C Within the temperature range of and less than more than 600 DEG C 850 DEG C of temperature within the scope of there is at least one oxidation peak, and more than 350 DEG C The oxidation peak in maximum temperature in less than 850 DEG C of scope with peak is poor with the peak temperature of the oxidation peak having peak in minimum temperature For less than 300 DEG C.Above-mentioned low-crystalline carbon is noncrystalline or the low carbon of crystallinity.
According to the 2nd mode of the present invention, provide a kind of lithium ion battery as aforementioned 1st mode, C=O in aforementioned clad Oxygen containing ratio, in the total oxygen demand of aforementioned clad be 7atom%～39atom%.
According to the 3rd mode of the present invention, provide a kind of lithium ion battery as aforementioned 1st or the 2nd mode, aforementioned clad Low-crystalline carbon be amorphous carbon.
According to the 4th mode of the present invention, provide the lithium ion battery of either type in a kind of such as the aforementioned 1st～the 3rd, aforementioned The ratio of C-OH and C=O in clad, is calculated as 1 with the atomic composition ratio of oxygen in each functional group：1～4：1.Aforementioned C-OH and C= The ratio of O, in terms of the oxygen atom ratio of components in each functional group, preferably 1：1～2：1.
According to the 5th mode, provide the lithium ion battery of either type in a kind of such as the aforementioned 1st～the 4th, aforementioned negative electrode active Material passes through calculated by X-ray diffraction method（002）Face interval d002 is 0.3354nm～0.3370nm, and crystallite dimension Lc is 20nm～90nm.
According to the 6th mode, provide the lithium ion battery of either type in a kind of such as the aforementioned 1st～the 5th, aforementioned clad Thickness is 10nm～100nm.
According to the 7th mode, provide the lithium ion battery of either type in a kind of such as the aforementioned 1st～the 6th, aforementioned negative electrode active The strength ratio of the Raman peaks of material（I1360/I1580) it is 0.1～0.7.
According to the 8th mode, provide the lithium ion battery of either type in a kind of such as the aforementioned 1st～the 7th, aforementioned negative electrode active The irreversible capacity of material unit mass is 20mAh/g～31mAh/g, and the discharge capacity density of negative electrode active material For 350mA/g～365mA/g.
According to the 9th mode, provide the lithium ion battery of either type in a kind of such as the aforementioned 1st～the 8th, foregoing graphites core material Expect the graphite particle for having carried out isotropism pressurized treatments.
According to the 10th mode, provide the lithium ion battery of either type in a kind of such as the aforementioned 1st～the 8th, aforementioned clad It is to be thermally decomposed in non-oxidizing atmosphere and by aforementioned low-crystalline carbon front by making organic compound or its mixture The carbon coating being formed is stated on the surface of graphite nuclear material.
According to the 11st mode, provide a kind of lithium ion battery as aforementioned 10th mode, aforementioned clad is by connecing Under the conditions of touching, aforementioned organic compound or its mixture are thermally decomposed the carbon coating of gained with foregoing graphites nuclear material.
According to the 12nd mode, provide a kind of lithium ion battery as aforementioned 10th or the 11st mode, aforementioned organic compound It is the organic high molecular compound with liquid phase carbonation.
According to the 13rd mode, provide a kind of lithium ion battery as aforementioned 10th or the 11st mode, aforementioned organic compound It is with the organic resin of solid phase carbonization.
According to the 14th mode, provide the lithium ion battery of either type in a kind of such as the aforementioned 1st～the 13rd, aforementioned low crystallization Property containing ratio in aforementioned compound carbon particle for the carbon be foregoing graphites nuclear material and aforementioned low-crystalline carbon total quality 0.1 Quality %～20 mass %.
According to the 15th mode, provide the lithium ion battery of either type in a kind of such as the aforementioned 1st～the 14th, aforementioned positive electrode bag Containing positive active material, conductive auxiliary agent, positive electrode binder and collector.
According to the 16th mode, provide the lithium ion battery of either type in a kind of such as the aforementioned 1st～the 15th, aforementioned positive electrode bag Containing positive active material, conductive auxiliary agent, positive electrode binder and collector, this positive active material is selected from LiCoO2、 LiNiO2、LiMn2O4、LiMnO3、LiMn2O3、LiMnO2、Li4Mn5O12、LiMn2-xMxO2（Wherein, M=Co, Ni, Fe, Cr, Zn or Ta；X=0.01～0.2）、Li2Mn3MO8（Wherein, M=Fe, Co, Ni, Cu or Zn）、Li1-xAxMn2O4（Wherein, A=Mg, B, Al, Fe, Co, Ni, Cr, Zn or Ca；X=0.01～0.1）、LiNi1-xMxO2（Wherein, M=Co, Fe or Ga；X=0.01～0.2）、 LiFeO2、Fe2（SO4）3、LiCo1-xMxO2（Wherein, M=Ni, Fe or Mn；X=0.01～0.2）、LiNi1-xMxO2（Wherein, M=Mn, Fe, Co, Al, Ga, Ca or Mg；X=0.01～0.2）、Fe（MoO4）3、FeF3、LiFePO4And LiMnPO4In the group being formed extremely Few one kind.
According to the 17th mode, provide the lithium ion battery of either type in a kind of such as the aforementioned 1st～the 16th, aforementioned positive electrode bag Containing positive active material, conductive auxiliary agent, positive electrode binder and collector, this positive active material is LiNi1/3Mn1/3Co1/3O2.
According to the 18th mode, provide a kind of lithium ion battery by either type in more than 2 such as the aforementioned 1st～the 17th with The battery module that series, parallel or connection in series-parallel form are formed by connecting.
According to the 19th mode, provide a kind of being connected to the battery module of aforementioned 18th mode by outside terminal can Moving body accumulating system in the charge-discharge circuit being connected with external equipment or fixed accumulating system.
Invention effect
According to the present invention it is possible to provide a kind of lithium ion battery that improve cycle life and High temperature storage characteristic, use The battery module of this lithium ion battery and moving body accumulating system or fixed accumulating system.Brief description
Fig. 1 represents a kind of form of the cross-sectional configuration of the lithium ion battery being applied to the present invention.
Fig. 2 is that the differential thermal thermogravimetric of the negative electrode active material representing the embodiment of the present invention 4 measures simultaneously（TG-DTA）Result Figure.
Fig. 3 is that the differential thermal thermogravimetric of the negative electrode active material representing the embodiment of the present invention 3 measures simultaneously（TG-DTA）Result Figure.
Fig. 4 is the plane skeleton diagram representing the lithium ionic cell module being applied to the present invention.
Specific embodiment
The alternate manner of the present invention is known by described further below.In the present invention, term used is made with its usual implication With.
In this manual, term " operation " not only comprises independent operation, even and if cannot be bright with other operations When really distinguishing, as long as can reach the predictive role of this operation, just it is also contained in this term.
Additionally, in the present invention, use "～" represented by numerical range, represent and comprise "～" before and after described numerical value Scope respectively as minima and maximum.
Further, in the present invention, when referring to the amount of each composition in compositionss, there is multiple being equivalent in the composition In the case of the material of each composition, unless otherwise specified, then refer to the total amount of the plurality of material present in compositionss.
In the present invention, comprise the clad coated graphite particle with low-crystalline carbon（Graphite nuclear material）Composite carbon Particle, and make the oxygen concentration in this clad be particular range.Thus, it is possible to provide a kind of lithium ion battery, it contains negative Pole, positive pole, nonaqueous electrolyte and nonaqueous solvent, described negative pole is included in thermogravimetric algoscopy, more than 350 DEG C and less than 600 DEG C low-temperature region in there is at least one oxidation peak（The peak of the temperature differential value of weight change）, more than 600 DEG C 850 DEG C with Under high-temperature area in there is at least one oxidation peak（The peak of the temperature differential value of weight change）, and 850 more than 350 DEG C The oxidation peak having peak in maximum temperature in scope below DEG C poor with the peak temperature of the oxidation peak in minimum temperature with peak is Less than 300 DEG C of compound carbon particle is as negative electrode active material.The lithium ion battery of the present invention, is High temperature storage characteristic and circulation The battery of excellent.
The compound carbon particle of the present invention, is the material of the clad coated graphite nuclear material by low-crystalline carbon, And constitute negative electrode active material.So-called low-crystalline carbon, including noncrystalline or mesomorphic carbon（The low-down carbon of crystallinity, by X Ray diffraction method substantially cannot confirm peak crystallization）.This low-crystalline carbon coating can be obtained by various methods, will be permissible It is made to separate out on graphite nuclear material so that the organic substance of liquid phase thermal decomposition heats in non-oxidizing atmosphere.
Foregoing graphites nuclear material has preferably carried out the graphite particle of isotropism pressurized treatments.Additionally, aforementioned low crystallization The clad of property carbon can also be by make organic compound or its mixture thermally decomposed in non-oxidizing atmosphere and The low-crystalline carbon coating being formed on the surface of foregoing graphites nuclear material.
Additionally, aforementioned organic compound or its mixture can be heat point under conditions of contacting with foregoing graphites nuclear material The material of solution, the organic resin with the organic high molecular compound of liquid phase carbonation or with solid phase carbonization.Aforementioned clad is preferably 0.1 mass %～20 mass % of total quality of foregoing graphites nuclear material and aforementioned low-crystalline carbon.
The present invention can be applied at least 2 above-mentioned lithium ion batteries so that series, parallel or connection in series-parallel form connect The discharge and recharge that the battery module and being connected to above-mentioned battery module by outside terminal becoming can be connected with external equipment is electric They are hereinafter also specifically described by the moving body accumulating system in road or fixed accumulating system.
Embodiment
（Embodiment 1）
Fig. 1 schematically show the internal structure of the lithium ion battery 101 of the drum of one embodiment of the invention. 110 is positive pole, and 111 is dividing plate, and 112 is negative pole, and 113 is battery can, and 114 is positive pole current collections piece, and 115 is negative pole collector plate, 116 It is inner cap, 117 is intrinsic pressure relief valve, 118 be packing ring, 119 be positive temperature coefficient（PTC：Positive temperature coefficient）Resistive element, 120 is battery cover.Battery cover 120 be by inner cap 116, intrinsic pressure relief valve 117, packing ring 118, The unitary member that PTC resistor element 119 is constituted.
Positive pole 110 is made up of positive active material, conductive auxiliary agent, positive electrode binder and collector.Illustrate this positive-active During material, LiCoO can be enumerated2、LiNiO2And LiMn2O4As representative examples.In addition, LiMnO can also be enumerated3、 LiMn2O3、LiMnO2、Li4Mn5O12、LiMn2-xMxO2（Wherein, M=Co, Ni, Fe, Cr, Zn or Ta；X=0.01～0.2）、 Li2Mn3MO8（Wherein, M=Fe, Co, Ni, Cu or Zn）、Li1-xAxMn2O4（Wherein, A=Mg, B, Al, Fe, Co, Ni, Cr, Zn or Ca；X=0.01～0.1）、LiNi1-xMxO2（Wherein, M=Co, Fe or Ga；X=0.01～0.2）、LiFeO2、Fe2（SO4）3、 LiCo1-xMxO2（Wherein, M=Ni, Fe or Mn；X=0.01～0.2）、LiNi1-xMxO2（Wherein, M=Mn, Fe, Co, Al, Ga, Ca or Mg；X=0.01～0.2）、Fe（MoO4）3、FeF3、LiFePO4And LiMnPO4Deng.In the present embodiment, from high-energy can be realized Density and from the viewpoint of the excellent cycling life-span, selects LiNi1/3Mn1/3Co1/3O2As positive active material.But, the present invention Positive electrode be not subject to any restriction, be therefore not limited to these materials.
The particle diameter of positive active material is defined as comprising the mixture layer of positive active material, conductive auxiliary agent and positive electrode binder Thickness below.When there are the coarse grain with mixture layer thickness dimensions above in positive electrode active material powder, beforehand through Sieve classification, air classification etc. remove coarse grain, make the particle of below mixture layer thickness.
Further, since positive active material is oxide system and resistance height, hence with by for supplementing its electric conductivity The conductive auxiliary agent that carbon dust is constituted.Thus have the advantages that the low resistive of positive pole or battery behavior improve.Conductive auxiliary agent, can With using material with carbon elements such as acetylene black, white carbon black, graphite, amorphous carbons, or their combinations of more than two kinds.In order in the internal shape of positive pole Become electronic network it is desirable to the particle diameter of conductive auxiliary agent is less than the mean diameter of positive active material, for less than the 1/10 of its mean diameter.
Because positive active material and conductive auxiliary agent are all powder, therefore positive electrode binder is mixed in powder, and Powder is made to be bonded on collector while being bonded to each other.
The aluminium foil that collector can be 10 μm～100 μm using thickness or thickness are 10 μm～100 μm and have a diameter of The aluminum perforated foil in the hole of 0.11mm～10mm, expansion alloy（Expand metal）, or foamable metal sheet etc., its material except Beyond aluminum, rustless steel and titanium etc. can also be suitable for.In the present invention, material, shape, manufacture method etc. do not limit, and can make Use arbitrary collector.
In order to make positive pole 110, need to modulate anode sizing agent.Illustrate its composition when, positive active material be 89 mass parts, Acetylene black is 4 mass parts, PVDF（Kynoar）Positive electrode binder be 7 mass parts, but the species according to material, specific surface Long-pending, particle diameter distribution etc. and change, be not limited to the composition illustrated.The solvent of anode sizing agent, as long as dissolving positive electrode binder Solvent, and for PVDF positive electrode binder, how using METHYLPYRROLIDONE.And, bonded according to positive pole The species of agent, suitably selects solvent.For the decentralized processing of positive electrode, using known kneading machine, dispersion machine.
Mixing is made to have disperseed positive active material, conductive auxiliary agent, positive pole bonding by doctor blade method, infusion process, nebulization etc. The anode sizing agent of agent and solvent is attached on collector, then solvent is dried, and carries out extrusion forming by roll-in to positive pole, by This forms the mixture layer comprising positive active material, conductive auxiliary agent and positive electrode binder on the current collector, can by above step To make positive pole.Additionally, by carrying out repeatedly from being applied to dry step it is also possible to make multiple mixture layer layer on the current collector Dissolve.
Negative pole 112 is made up of negative electrode active material, negative electrode binder and collector.Negative electrode active material, has in graphite Nuclear material（Graphite particle）Surface on define the nucleocapsid structure of clad.As negative electrode active material, it is possible to use energy Enough adsorb and release the negative electrode active material of lithium, negative electrode active material is that have low knot on the surface of graphite nuclear material The compound carbon particle of the clad of crystalline substance carbon, the surface of aforementioned clad has C=O, C-OH and C-O functional group, aforementioned bag Oxygen atom containing ratio in the total amount of the carbon atom of coating and oxygen atom is 2atom%～5atom%, and aerial thermogravimetric measures In method, negative electrode active material respectively 350 DEG C more but less than 600 DEG C within the temperature range of and more than 600 DEG C 850 DEG C with Under temperature within the scope of have at least one oxidation peak, and less than 850 DEG C of scope more than 350 DEG C maximum temperature have The oxidation peak at peak is had to be less than 300 DEG C with the peak temperature difference of the oxidation peak in minimum temperature with peak.Specifically, using aftermentioned The negative electrode active material manufacturing in each embodiment, and make lithium ion battery for each negative electrode active material.
In order to make negative pole 112, need to modulate cathode size.Illustrate its composition when, negative electrode active material be 95 mass parts, PVDF（Kynoar）Positive electrode binder be 5 mass parts, but the species according to material, specific surface area, particle diameter distribution etc. and change Become, be not limited to the composition illustrated.The solvent of cathode size, as long as the solvent of dissolving negative electrode binder, and for PVDF negative electrode binder, how using METHYLPYRROLIDONE.And, the species according to negative electrode binder, suitably selects Solvent.For the decentralized processing of negative material, using known kneading machine, dispersion machine.
Mixing is made to have disperseed negative electrode active material, negative electrode binder and solvent by doctor blade method, infusion process, nebulization etc. Cathode size is attached on collector, then solvent is dried, and carries out extrusion forming by roll-in to negative pole, thus in collector Upper formation comprises the mixture layer of negative electrode active material, conductive auxiliary agent and negative electrode binder, can make negative pole by above step. Additionally, by carrying out repeatedly from being applied to dry step, multiple mixture layer stacking on the current collector can be made.
As shown in figure 1, inserting dividing plate 111 between positive pole 110 and negative pole 112, prevent the short of positive pole 110 and negative pole 112 Road.Dividing plate 111 can use the polyolefin polymeric membrane being formed by polyethylene, polypropylene etc., or makes polyolefin high Molecule and the fluorine system polymeric membrane with politef as representative fuse micro-porous film of multiple structure of gained etc..Due to these Dividing plate 111 needs to pass through lithium ion in battery charging and discharging, it is often desirable to having the pore that aperture is 0.01 μm～10 μm, And the porosity is 20%～90%.Additionally, in order that dividing plate 111 does not shrink when battery temperature raises, can also be in dividing plate 111 Surface on lamelliform formed pottery and organic resin system binding agent mixture.In the following description, will be by positive pole 110th, the Construction integration thing that negative pole 112 and dividing plate 111 are formed is referred to as electrode group.
In addition, dividing plate 111 is also inserted into being configured between the electrode of electrode group end and battery can 113, and pass through battery Tank 113 makes positive pole 110 and the negative pole 112 will not short circuit.Additionally, in dividing plate 111 and each electrode（Positive pole 110, negative pole 112）Surface Inside pore, maintain the electrolyte being made up of electrolyte and nonaqueous solvent.
The top of electrode group, is electrically connected with outside terminal by lead.Positive pole 110 passes through positive pole current collections piece 114 and battery Lid 120 connection.Negative pole 112 is connected with battery can 113 by negative pole collector plate 115.In addition, positive pole current collections piece 114, negative pole current collection Piece 115, can adopt the arbitrary shape such as wire, tabular.As long as the structure of ohmic loss can be reduced when flowing through electric current, and The material do not reacted with electrolyte, then positive pole current collections piece 114, the shape of negative pole collector plate 115 and material are arbitrary.
Winding form shown in Fig. 1 for the structure of electrode group is it is also possible to make arbitrary shape according to battery can 113 shape Shape.If battery can 113 is square, the shape that positive pole 110, negative pole 112 and dividing plate 111 are laminated can be changed into, or Shape with flat winding.
The material of battery can 113 has the material of corrosion resistance selected from aluminum, rustless steel, nickel-plated steel etc. to nonaqueous electrolyte. Additionally, when electrically connecting positive pole current collections piece 114 or negative pole collector plate 115 with battery can 113, selecting the material of piece, so that Contact with nonaqueous electrolyte partly in, the change of material will not be led to because of the alloying of the burn into of battery can 113 and lithium ion Matter.
Then, make battery cover 120 closely sealed with battery can 113, will be airtight for battery entirety.In the case of Fig. 1 shape, can adopt Method with riveting.In addition to this method, method airtight for battery also had the known technologies such as welding, fusion.
As the typical example of the electrolyte that can use in the present invention, have by dimethyl carbonate, diethyl carbonate, carbonic acid Ethyl methyl ester or their of more than two kinds combination etc. with dissolved in the solvent of ethylene carbonate mixing gained as electrolyte six Lithium fluophosphate（LiPF6）Or boron lithium fluoride（LiBF4）Solution.The present invention to solvent, the species of electrolyte, solvent mixing ratio Do not limit, other electrolyte can also be utilized.Electrolyte can also be included in Kynoar, polyethylene glycol oxide etc. from State in sub- conducting polymer uses.At this moment it is not necessary to aforementioned separator plate.
In addition, can be used in the solvent of electrolyte, there are propylene carbonate, ethylene carbonate, butylene carbonate, carbonic acid Asia second Alkene ester, gamma-butyrolacton, dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate, 1,2- dimethoxy-ethane, 2- methyl four Hydrogen furan, dimethyl sulfoxide, 1,3- dioxolanes, Methanamide, dimethylformamide, methyl propionate, ethyl propionate, tricresyl phosphate Ester, trimethoxy-methane, dioxolanes, diethyl ether, sulfolane, 3- methyl -2- oxazolidone, oxolane, 1,2- bis- The nonaqueous solvents such as Ethoxyethane, chlorocarbonic acid ethyl and chlorocarbonic acid Asia propyl ester.They can be used alone or by 2 kinds with On be applied in combination.As long as will not decompose on the built-in negative or positive electrode of battery of the present invention, then can be molten using in addition Agent.
Additionally, electrolyte has LiPF6、LiBF4、LiClO4、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6Or with trifluoro Sulfonyl methane imine lithium is multiple lithium salts such as imide salts of the lithium of representative.They can be used alone or combine two or more Use.These salt can be dissolved in made nonaqueous electrolytic solution in above-mentioned solvent and be used as battery electrolytic solution.As long as will not The built-in negative or positive electrode of the battery of the present embodiment decomposes, then can be using electrolyte in addition.
Using solid macromolecule electrolyte（Polymer dielectric）When, can be by ethylene oxide, acrylonitrile, inclined fluorine second The ionic-conductive polymer that the monomers such as alkene, methyl methacrylate, hexafluoropropene are polymerized gained is used as electrolyte.They are permissible It is used alone or two or more is applied in combination.When using these solid macromolecule electrolytes, have and can omit aforementioned separator plate 111 advantage.
Further, it is also possible to use ionic liquid.For example, it is possible to from 1- ethyl-3-methylimidazole tetrafluoroborate （EMI-BF4）；Lithium salts LiN（SO2CF3）2（LiTFSI）Mixed complex with triethylene glycol dimethyl ether. and tetraethylene glycol dimethyl ether；With And cyclic quaternary cation（N- Methyl-N-propyl pyrrolidine can be illustrated）With imide series anion（Can illustrate double （Trifluoromethane sulfonyl group）Acid imide）Combination and on negative or positive electrode not resolvent combination in select and be used for this Bright lithium ion battery.They may be used singly or in combination of two or more.
In the state of the method for implanting of electrolyte has and pulls down by battery cover 120 from battery can 113, it is directly appended to electricity Method in the group of pole.When having liquid injection port on battery cover 120, there is the method added from this liquid injection port.
Solid macromolecule electrolyte can also be used（Polymer dielectric）Or gel electrolyte replaces nonaqueous electrolytic solution. Solid macromolecule electrolyte can also use the known polymer dielectric such as polyethylene glycol oxide or Kynoar and non-water power The mixture of solution liquid（Gel electrolyte）.Further, it is also possible to use ionic liquid.
（Embodiment 2）
The present embodiment, in addition to the item of following special record, and embodiment 1 is same.
<The modulation of graphite nuclear material>
Graphite nuclear material used in embodiment 2, using by the Delanium manufactured by isotropism pressurized treatments, but The present invention is not limited to this material.So-called isotropism pressurized treatments herein, are not the pressurizations only from specific direction（Each to Different in nature pressurized treatments）, but the generally known process pressurizeed from all directions.If carried out to carbon dust like this Isotropism pressurized treatments, then the compound heap density of carbon particle of the used as negative electrode of Li-ion battery of gained and the flowing of cathode size Property improve, the density variation of the lithium ion battery negative produced is little, and improves with the adaptation of negative electrode collector.Therefore, The cycle characteristics of the lithium ion battery of gained can be improved.
As the method for the isotropism pressurized treatments of carbon dust, as long as the method for isotropism pressurization can be carried out just Be not particularly limited, for example can enumerate carbon dust is added in the container of rubber-type etc. and quiet as pressure medium using water The pressurization of hydraulic pressure isotropism, using gases such as air as the isotropism of the utilization air pressure of pressure medium pressurization etc. at pressurization Reason.
As the pressure of the pressure medium of the isotropism pressurized treatments of carbon dust, preferably 4.9 × 106Pa～1.96 × 108Pa（50kgf/cm2～2000kgf/cm2）Scope, more preferably 1.96 × 107Pa～1.96 × 108Pa（200kgf/cm2 ～2000kgf/cm2）Scope, and be more preferably 4.9 × 107Pa～1.77 × 108Pa（500kgf/cm2~ 1800kgf/cm2）Scope.If pressure is 4.9 × 106Pa（50kgf/cm2）More than, then rewarding lithium ion battery Cycle characteristics improves the tendency that effect increases.If additionally, pressure is 1.96 × 108Pa（2000kgf/cm2）Hereinafter, then can press down The specific surface area that the used as negative electrode of Li-ion battery of gained processed is combined carbon particle expands, and therefore has the lithium-ion electric that can reduce gained The tendency of the irreversible capacity of the first circulation in pond.
When as mentioned above isotropism pressurized treatments being implemented to carbon dust, due to particle easily coagulation each other, therefore excellent After being selected in isotropism pressurized treatments, carry out crushing, sieve etc. and processing.In addition, when particle non-coagulation each other it is also possible to not enter Row is broken.
By above method, cycle characteristics etc. can be greatly improved, and carry out isotropism pressurized treatments and make Used as negative electrode of Li-ion battery is combined carbon particle（Negative electrode active material）, the interfloor distance d of its crystal（002）Can be The scope of 0.3354nm～0.3370nm, C axial crystallite dimension Lc（002）It can be the scope of 20nm～90nm.Crystal Interfloor distance d（002）And C axial crystallite dimension Lc is obtained by X-ray diffraction method.This X-ray diffraction method according to Shake（JSPS, JSPS）Method is measured.
As the material with carbon element of above-mentioned isotropism pressurized treatments object, it is not particularly limited, native graphite can be enumerated, incite somebody to action The Delanium of coke graphitization gained, organic system macromolecular material, by the Delanium of the graphitization gained such as Colophonium, noncrystalline Carbon, K cryogenic treatment carbon etc., wherein preferred Delanium.
Delanium, is can to add bonding main material in graphited main material to coke powder, resin carbon compound etc. Form the Colophonium of molded body, tar, and organic based material such as thermosetting resin, thermoplastic resin, a part of stone as needed Powdered ink end, and the catalyst promoting graphitization reaction（Graphitization catalyst）, and by these raw mixtures 2500 DEG C with Carry out graphitization calcining at a temperature of upper.Can be by the graphite calcined body of gained through pulverizing process, making artificial graphite.Pass through The crystallinity of the Delanium of above method gained is easily improved, and can improve the discharge capacity of the lithium ion battery of gained.
Herein, as graphitization catalyst, the preferably metal such as Ti, Si, Fe, Ni, B or its oxide or carbide.Graphite Change catalyst, preferably state before combination and add when main material and aforementioned organic based material, and mixed simultaneously.The temperature of mixing It is preferably the temperature of aforementioned organic system material softening melting, this temperature is different according to material therefor, but preferably 50 DEG C～350 DEG C scope.Additionally, when aforementioned organic based material is made by solution by solvent etc., can admixed graphite urge at normal temperatures Agent.
Additionally, in the manufacturing process of Delanium, can by this raw mixture at a temperature of more than 2500 DEG C Before graphitization, carry out pulverizing, molding, and carry out precalcining at a temperature of 700 DEG C～1300 DEG C about further.Additionally, Sequence of steps can also be changed, after precalcining at a temperature of 700 DEG C～1300 DEG C about, pulverized, and grain will be have adjusted Degree powder body more than 2500 DEG C at a temperature of carry out graphitization calcining.Calcining heat during graphitization, from the graphite nuclei of gained From the viewpoint of the crystallinity of material and discharge capacity, preferably more than 2500 DEG C, more preferably more than 2800 DEG C, and further It is preferably more than 3000 DEG C.Atmosphere during calcining, as long as being difficult to the condition aoxidizing, is just not particularly limited, for example, it is possible to row Lift medium from escaping gas atmosphere, nitrogen atmosphere, argon atmosphere, vacuum.
During above-mentioned precalcining, organic based material such as fragrant family organic molecule, coal tar or Colophonium is heating up During temporarily first melt, volatile ingredient depart from, condensation and carbonization.
As the breaking method of graphitization calcined body, it is not particularly limited, for example, can adopt jet mill, hammer mill, pin The impact comminution mode such as excellent pulverizer.After pulverizing, adjust granularity, make graphite particle.In addition, pulverizing before graphitization and adjusting During whole granularity, just can not be pulverized after graphitization.
Using the graphite particle of Delanium fabricated as described above, implement isotropism pressurized treatments, form graphite nuclei Material.Additionally, by coating low-crystalline carbon described later, being formed and be suitable for cycle characteristics and fast charging and discharging excellent Lithium ion battery used as negative electrode of Li-ion battery be combined carbon particle.
<The formation of clad>
Herein, as the process of cladding low-crystalline carbon, for example, it is possible to enumerate to having disperseed the specific of graphite nuclear material to have Machine solvent applies the process of ultrasound wave.In this process, first pass through traveling wave type ultrasonic and apply to make organic solvent carbonization and separate out. It is to produce on the surface of scattered graphite nuclear material due to separating out, therefore on the surface of graphite nuclear material, can be formed The carbon layer of unadsorbed useless functional group etc..As above-mentioned specific organic solvent, such as o-dichlorohenzene etc. can be enumerated, at this In embodiment, using o-dichlorohenzene.
Then, in order to make the carbon layer of precipitation adhere on the surface of graphite nuclear material by thermal decomposition, form low crystallization The clad of property carbon, and carry out heat treated.Heat treatment temperature is different according to parent material, but preferably 400 DEG C～800 DEG C scope, and the particularly desirable scope being set as 550 DEG C～750 DEG C.Atmosphere during heat treated is highly desirable to be by nitrogen The non-active gas atmosphere that gas, rare gas are constituted.In the present embodiment, processed in the state of so that nitrogen is circulated. By so being processed, clad and the burning of graphite nuclear material can be prevented.Additionally, it is micro importing in clad Oxygen, and when actively importing carboxyl, hydroxyl, can be in the non-oxygen mixing less than 10% micro amount of oxygen and non-active gas The oxygen concentration of clad is adjusted under the property changed atmosphere.
In addition, as the method unlike those described above that clad is formed on graphite nuclear material, can also use other Organic high molecular compound forms clad as the parent material of low-crystalline carbon.As organic high molecular compound, can To enumerate various Colophonium classes（Crude oil pitch, naphthabitumen, asphaltic pitches, coal tar asphalt, decomposition Colophonium etc.）Deng with liquid phase The organic high molecular compound of carbonization.It is dissolved in height boiling in the state of organic high molecular compound melting or organic high molecular compound In the state of point solvent, the clad of low-crystalline carbon is formed by heat resolve on graphite nuclei material surface.Or, also Can be gathered using phenolic resin, furfuryl alcohol resin, celluosic resin, polyacrylonitrile and polrvinyl chloride, polyvinylidene chloride, chlorination The ethylene halide base resin such as vinyl chloride and polyamide-imide resin, polyamide etc. are with the resin of solid phase carbonization.As The amount of the low-crystalline carbon on coated graphite nuclear material surface, with respect to the quality of the compound carbon particle of final gained, preferably 0.1 More than quality %, and consider from the balance of its covered effect and charge/discharge capacity, with respect to the quality of compound carbon particle, more preferably For 0.1 mass %～20 mass %, and it is more preferably 1 mass %～15 mass %.Thus, it is possible to will be by low-crystalline carbon institute shape The coating thickness becoming controls in 10nm～100nm.In addition, being combined the containing ratio of low-crystalline carbon in carbon particle in the present invention, Can be in the weight change determination using thermogravimetric analysiss, the value of the weight change amount corresponding to low-crystalline carbon is obtained.
In the present embodiment, using by the Delanium manufactured by isotropism pressurized treatments as graphite nuclear material, and The use of the thickness that o-dichlorohenzene makes clad is 10nm～100nm.Form heat treatment temperature during clad and be 550 DEG C, and lead to Cross and processed in nitrogen atmosphere and obtained compound carbon particle.
The thickness of clad, by with focused ion bundle processing unit (plant)（FIB）Negative electrode active material is cut out section, and makes Use transmission electron microscope（TEM）It is measured.According to locating, the thickness of clad there are deviation, and if bag The thickness of coating is at least more than 10nm, then speculate and electrolyte can be suppressed to pass through from the minim gap of clad.Thus may be used Prevent the end face directly contact of electrolyte and highly active graphite nuclear material, it can be considered that along with High temperature storage, charge and discharge The electrolyte decomposition reaction of electricity circulation reduces, and battery behavior improves.If additionally, the thickness of coating layer is below 100nm, wished Hope along with discharge and recharge reaction, lithium ion cladding layer segment mobile resistance less.
（Embodiment 3）
The present embodiment, in addition to the item of following special record, and embodiment 1 is same.
<The modulation of graphite nuclear material>
In embodiment 3, add as the coke powder being capable of graphited main material, be used for the work of coke powder that bonds For can the asphalt of graphited organic based material and the graphitization catalyst of ferrum system, manufacture Delanium.To with the addition of The material mixing of 1 mass %～50 mass % graphitization catalyst, after calcining and graphitization, is pulverized, and manufactures graphite.
In addition, the present invention does not limit to above-mentioned material.As being capable of graphited main material, it is possible to use fluid coke （fluid coke）, the various coke classes such as needle coke.As can graphited main material, from charge/discharge capacity and quickly fill From the viewpoint of flash-over characteristic, preferably comprise coke powder, and more preferably comprise needle coke powder.Further, it is also possible to add Graphited material with carbon element to use as part main material for native graphite, Delanium etc..As above-mentioned for the master that bonds What raw material formed forming graphite body being capable of graphited organic based material, it is possible to use coal system, petroleum, artificial etc. various Colophonium, coal tar.As graphitization catalyst, it is possible to use ferrum, nickel, titanium, boron, silicon etc., their oxide, carbide, nitrogen Compound etc..
Graphited main material can be mixed with above-mentioned by being possible to graphited organic based material, gained can be reduced Graphite particle（Graphite nuclear material）Draw ratio, and set can be made or combine the granular graphite of multiple flat particles Son.It is thus possible to improve the fast charging and discharging characteristic of lithium ion battery making and cycle characteristics.
Additionally, as aforementioned can graphited organic based material, in addition to Colophonium, coal tar, can also using heat Organic based material such as thermosetting resin, thermoplastic resin.As the addition being capable of graphited organic based material, had according to used The carbon yield of machine based material and cohesive force and different, for example, when using Colophonium, can be graphited with respect to 100 mass parts Main material, preferably 10 mass parts～100 mass parts, more preferably 10 mass parts～70 mass parts, and be more preferably 10 Mass parts～50 mass parts.
The mixing ratio of graphitization catalyst, can be according to target graphite particle（Graphite nuclear material）Particularly particle special Property selecting, mix with respect to the raw material that organic based material such as the main materials such as coke, Colophonium and graphitization catalyst are combined The gross mass of thing, preferably adds 1 mass %～50 mass % graphitization catalyst.The mixing ratio of graphitization catalyst, Ke Yigen According to target graphite particle（Graphite nuclear material）Particularly particle propertiess selecting.For graphitization catalyst, if its Addition is more than 1 mass %, then the crystal growth of graphite particle is good, and charge/discharge capacity improves, and can increase gained Lithium ion battery discharge capacity.On the other hand, if the amount of graphitization catalyst is below 50 mass %, easily uniform Mixing, and the characteristic deviation of the graphite particle of operability variation and gained can be avoided to expand.Especially, graphitization is urged The addition of agent is more preferably below 10 mass %, below more preferably 5 mass %, and is still more preferably 1 mass % ～5 mass %.If increasing the addition of graphitization catalyst within the above range, having the tendency of discharge capacity increases, and such as Fruit reduces its addition within the above range, then have the tendency of specific surface area and reduce and the raising of heap density.
Additionally, as graphitization catalyst, the preferably metal such as Ti, Si, Fe, Ni, B, or its oxide or carbide, and excellent It is selected in when mixing main material and organic based material and add and mix simultaneously.
Temperature during above-mentioned middle admixed graphite catalyst, is preferably capable graphited aforementioned organic system material softening and melts The temperature melted.This temperature is different according to material therefor, but preferably 50 DEG C～350 DEG C of scope.Additionally, by solvent etc. Allow to graphited organic based material to be formed during solution it is also possible to mix at normal temperatures.
Then, be possible to graphited main material, can graphited organic based material, graphitization catalyst mixing gained Raw mixture, preferably precalcining at 500 DEG C～2000 DEG C, and pulverize this calcined material further, adjustment mean diameter is extremely 10 μm～100 μm, further more than 2500 DEG C at a temperature of carry out graphitization.
Precalcining temperature before pulverizing is preferably 500 DEG C～1500 DEG C, more preferably 700 DEG C～1500 DEG C.If pulverized Front precalcining temperature is less than 2000 DEG C, then the graphite particle of gained（Graphite nuclear material）Heap density high, and specific surface area Little, and also have the tendency of draw ratio reduction.If additionally, the precalcining temperature before pulverizing is more than 500 DEG C, the energy adding The carbonization of enough graphited organic based materials fully, therefore has and can suppress what particle was bonded to each other to incline after pulverizing graphitization To.Additionally, before precalcining, can also as needed aforementioned base materials mixture forming be suitable shape.Precalcining is excellent Be selected in aforementioned base materials mixture to be difficult to carry out in the atmosphere aoxidizing, for example, it is possible to be set forth in nitrogen atmosphere, in argon atmosphere, The method of calcining in vacuum.
Then carry out graphitization processing.Graphitizing method is not particularly limited, for example, from the graphite particle of gained From the viewpoint of crystallinity and discharge capacity, preferably medium from escaping gas atmosphere, nitrogen atmosphere, argon atmosphere, vacuum Carry out at a temperature of more than 2500 DEG C.Graphitization temperature, more preferably more than 2700 DEG C, more preferably 2900 DEG C with On, and it is particularly preferably more than 3000 DEG C.As the upper limit of graphitization temperature, preferably less than 3200 DEG C.Graphited temperature Higher, then the crystal growth of graphite is good, and also graphitization catalyst is difficult in the graphite particle remain in making simultaneously, and The tendency of charge/discharge capacity all raisings in any case.
After graphitization processing, carry out pulverization process.Method as pulverizing, is not particularly limited, it is for instance possible to use spray Penetrate the impact comminution method such as mill, hammer mill, sprayer of hammer crusher.
<The formation of clad>
As described below, in the graphite particle of above-mentioned gained（Graphite nuclear material）Upper cladding low-crystalline carbon.For as bag Cover the species of the organic high molecular compound of the parent material of low-crystalline carbon of graphite nuclear material and by its carbonization gained For the covering amount of low-crystalline carbon, it is not particularly limited.As organic high molecular compound, various Colophonium classes can be enumerated （Crude oil pitch, naphthabitumen, asphaltic pitches, coal tar asphalt, decomposition Colophonium etc.）Deng with the organic polymer of liquid phase carbonation Compound.Or, phenolic resin, furfuryl alcohol resin, celluosic resin, polyacrylonitrile and polrvinyl chloride can be enumerated, gather inclined dichloro The ethylene halide base resin such as ethylene, chliorinated polyvinyl chloride.As the amount of the low-crystalline carbon on coated graphite nuclear material surface, relatively More than the quality of the compound carbon particle of final gained, preferably 0.1 mass %, and from its covered effect and charge/discharge capacity Balance considers, more preferably 0.1 mass %～20 mass %, and is more preferably 1 mass %～15 mass %.Thus, it is possible to will Controlled in 10nm～100nm by the coating thickness that low-crystalline carbon is formed.
In embodiment 3, using carboxymethyl cellulose resin, and make clad thickness be 10nm～100nm, formed bag Heat treatment temperature during coating is 750 DEG C.Atmosphere is nitrogen.
The thickness of clad, by negative electrode active material being cut out section with FIB, and is measured using TEM.According to survey Positioning is put, and the thickness of clad there are deviation, and if the thickness of coating layer is at least more than 10nm, then speculates and can suppress Electrolyte passes through from the minim gap of clad.Electrolyte thus can be prevented direct with the end face of highly active graphite nuclear material Contact, it can be considered that the electrolyte decomposition reaction along with High temperature storage, charge and discharge cycles reduces, battery behavior improves. If additionally, the thickness of coating layer be below 100nm it would be desirable that along with discharge and recharge reaction, lithium ion cladding layer segment Mobile resistance less.
（Embodiment 4）
The present embodiment, in addition to the item of following special record, and embodiment 1 is same.
<The modulation of graphite nuclear material>
Graphite nuclear material used in embodiment 4, is the material with carbon element with graphene-structured.That is, it is possible to use Electrochemistry can adsorb and release the native graphite of lithium ion, Delanium, mesocarbon, expanded graphite, carbon fiber, gas The carbonaceous materials such as phase growth method carbon fiber, asphalt series carbonaceous material, needle coke, petroleum coke, carbonized polyacrylonitrile fibre, carbon black Material, or by thermal decomposition, the ring type hydrocarbon of 5 yuan of rings or 6 yuan of rings or ring type oxygen-containing organic compound are synthesized the amorphous carbon of gained Material etc..
Graphite nuclear material makes as follows.Mix the coke powder that 50 mass parts mean diameters are 5 μm, 20 mass parts tar drips Blue or green, 7 mass parts mean diameters are 48 μm of carborundum and 10 mass parts coal tar, and mix 1 hour at 200 DEG C.Pulverize institute Mixture, be press-formed into graininess, then in nitrogen atmosphere, calcine at 3000 DEG C.Gained is pulverized by hammer mill Calcined material, making mean diameter is 20 μm of graphite particle（Graphite nuclear material）.
Coke powder used herein is not limited to above-mentioned condition, can select 1 μm～tens μm of material.Additionally, Coke powder, the composition of tar asphalt can also suitably change.Other condition such as heat treatment temperature is also not limited to the above.
<The formation of clad>
The clad of low-crystalline carbon is formed on the graphite nuclear material that can make in example 4 by following steps. First, by the graphite particle of above-mentioned for 100 mass parts gained（Graphite nuclear material）Impregnate and be dispersed in 160 mass parts phenolic varnish types The methanol solution of phenolic resin（Hitachi Chemical Co., Ltd.'s system）In, make graphite particle phenolic resin blend molten Liquid.Filter this solution, being dried, carrying out heat treatment in the range of 800 DEG C～1000 DEG C, thus obtaining the table in graphite nuclear material The compound carbon particle of the clad of low-crystalline carbon is defined on face.Atmosphere is set to the addition of 0.5%～1% oxygen in nitrogen Mixed gas atmosphere（Non-oxidizing atmosphere）.Additionally, in addition to phenolic resin, naphthalene, anthracene, creosote can also be replaced with The Ppolynuclear aromatics such as oil.
Above-mentioned compound carbon particle is 3.6m by the specific surface area of BET method gained2/g.Additionally, passing through X-ray wide-angle diffraction The interfloor distance d002 of the graphite crystal of method gained is 0.3354nm～0.3370nm, and crystallite dimension Lc is the model of 20nm～90nm Enclose.Positioned at 1580cm-1And 1360cm-1Raman peaks strength ratio（I1360/I1580）Scope for 0.1～0.7.
Additionally it is possible to the method for coating of the low-crystalline carbon using other methods.For example also have and polyvinyl alcohol is coated In graphite particle（Graphite nuclear material）Go up the method so as to thermally decompose.At this moment, heat treatment temperature is wished for 500 DEG C～800 DEG C Scope.
Further, alternatively, can also directly add the particle of polrvinyl chloride, Polyvinylpyrrolidone etc., enter Row heat treatment.By these compounds and graphite particle（Graphite nuclear material）After mixing, it is heated to the temperature thermally decomposing, forms cladding Layer.
Additionally, in order to give oxygen until oxygen concentration necessary to the present invention to the clad of low-crystalline carbon, can also enter The capable oxidation processes employing ozone etc., corona treatment, ultraviolet（UV）The surface modifications such as process.Make covering material heat Less than 10% micro amount of oxygen during decomposition, can be added in non-active gas, and carry out surface modification using this mixed gas.
The clad of low-crystalline carbon is formed as mentioned above on graphite nuclei material surface, and with FIB, this powder is cut out Section, measures the thickness of carbon-coating using TEM.Although as a result, there is deviation, the thickness of the clad of low-crystalline carbon is The scope of 10nm～100nm.If the thickness of coating layer is more than 10nm, speculates and electrolyte can be suppressed micro- from clad Pass through in small-gap suture.The end face directly contact of electrolyte and highly active graphite nuclear material thus can be prevented, it can be considered that Electrolyte decomposition reaction along with High temperature storage, charge and discharge cycles reduces, and battery behavior improves.If additionally, coating layer Thickness be below 100nm it would be desirable that along with discharge and recharge reaction, lithium ion cladding layer segment mobile resistance less.
（Embodiment 5）
With the negative electrode active material to above-described embodiment 3 for the ozone（Compound carbon particle）Surface processed, make increase The negative electrode active material of oxygen content.In addition, and embodiment 3 is same.
（Embodiment 6）
In the cladding layer formation process of above-described embodiment 3, by the initial material of the low-crystalline carbon of coated graphite nuclear material Material is changed into crude oil pitch from carboxymethyl cellulose resin, makes negative electrode active material.In addition, and embodiment 3 is same.
（Comparative example 1）
The graphite nuclear material making in embodiment 4 is used as negative electrode active material.
<The evaluation of the negative electrode active material of embodiment 2～6>
（1）The evaluation of embodiment 4
In atmosphere to the negative electrode active material making in embodiment 4（Compound carbon particle）Carry out differential thermal thermogravimetric to measure simultaneously （TG-DTA）.The burning behavior reflection crystallinity of known material with carbon element, specific surface area, hence with the difference of this burning behavior, can To separate the oxidation peak of the carbon being derived from clad and the carbon from graphite nuclear material.It is known that the graphite usually from high crystalline Peak occur near 900 DEG C（Fig. 1 for example, with reference to Japanese Unexamined Patent Publication 2001-229914）, and low crystallization, Gao Bibiao Area, then get over and aoxidize under more lower temperature.Measure measure device using differential thermal thermogravimetric simultaneously, temperature of the measurement scope for room temperature～ 1100 DEG C, programming rate is 5 DEG C/min, and atmosphere is in the air, 80mL/min.Measure the aluminium oxide box that container uses 70 μ l, examination Sample quality is 10mg.
Show the result in Fig. 2.The TG-DTA data of Fig. 2, corresponds to the mensure knot of the compound carbon particle of table 1 embodiment 4 Really.Process weight change（The left longitudinal axis）, substantially constant below 350 DEG C, and weight starts when reaching more than 350 DEG C of temperature Slow minimizing, when about 700 DEG C, weight reaches zero（That is complete oxidation burning.）.At this moment the temperature of weight change is micro- Score value（The right longitudinal axis）, show two oxidation peak of the high-temperature area of low-temperature region near 411 DEG C and 678 DEG C.The former The oxidation reaction of clad, weight decrement at this moment is 10 mass %.It is contemplated that the clad of embodiment 4 is due on surface On there is oxygen functional group, therefore with general graphite-phase ratio it is easier to aoxidize at low temperature.In addition, the latter is graphite nuclear material Oxidation reaction.Belong to the temperature differential value peak of the weight change of this oxidation reaction（Right axle）For 678 DEG C, than general high knot The peak position of crystalline substance graphite material is lower.This is believed that the clad of embodiment 4 is high to the reactivity of oxygen, to by low crystallization Property carbon the oxidation reaction of inside graphite nuclear material that covers of clad create impact.
That is, the oxidation peak temperature with respect to clad（411℃）, the oxidation peak temperature of graphite nuclear material（678 ℃）Within 300 DEG C, this is one of feature of the present embodiment.Additionally, being combined the containing ratio of clad in carbon particle, be equivalent to Weight decrement with its oxidation reaction（10 mass %）, in the present embodiment, in compound carbon particle, low-crystalline carbon contains Rate is 0.1 mass %～20 mass %, and this is also another feature.
（2）The evaluation of embodiment 3
Then, Fig. 3 represents the negative electrode active material of the embodiment 3 changing clad formation condition（Compound carbon particle）'s Differential thermal thermogravimetric measures simultaneously（TG-DTA）Result.Weight change（The left longitudinal axis）, substantially constant below 450 DEG C, and reaching During more than 450 DEG C of temperature, weight starts slowly to reduce, and when about 900 DEG C, weight reaches zero（That is complete oxidation combustion Burn.）.At this moment the temperature differential value of weight change（The right longitudinal axis）, show 599 DEG C of low-temperature region and 801 DEG C of high-temperature area Two oxidation peak.The oxidation reaction of the former clad, weight decrement at this moment is 15 mass %.It is contemplated that implementing The clad of example 3, due to having oxygen functional group from the teeth outwards, therefore is easier to aoxidize than embodiment 4.
Additionally, belonging to the temperature differential value peak of the weight change of the latter's oxidation reaction（Right axle）Temperature（801℃）, than The oxidation peak position of general high crystalline graphite material is lower, and Fig. 2 is same.This is believed that the clad pair of embodiment 3 The reactivity of oxygen is high, creates impact to the oxidation reaction of the graphite nuclear material within clad.That is, with respect to cladding The oxidation peak temperature of layer（599℃）, the oxidation peak temperature of graphite nuclear material（801℃）Within 300 DEG C, this is the present embodiment One of feature.
Meanwhile, in TG-DTA determination data, at least in each temperature range of 400 DEG C～600 DEG C and 650 DEG C～850 DEG C Inside there is the oxidation peak of more than 1, each oxidation peak appears at and is observed that with respect to general high crystalline graphite material The appearance temperature of oxidation peak low temperature side, this is also another feature of the present embodiment.Additionally, clad in compound carbon particle Containing ratio, is equivalent to the weight decrement with its oxidation reaction（15 mass %）, in compound carbon particle, low-crystalline carbon contains Rate is 0.1 mass %～20 mass %, and this is also one of feature.
（3）The evaluation of embodiment 2
Negative electrode active material in embodiment 2（Compound carbon particle）Differential thermal thermogravimetric measure simultaneously（TG-DTA）In result, Obtain the oxidation peak from clad in 540 DEG C～560 DEG C of low temperature sides, come in 810 DEG C～830 DEG C of high temperature sides Oxidation peak from graphite nuclear material.Weight decrement with clad oxidation reaction is 1 mass %.It follows that embodiment 2 In the tendency of 2 oxidation peak of negative electrode active material and complex carbon material in low-crystalline carbon containing ratio all meet on State feature.
（4）The evaluation of embodiment 5
The negative electrode active material of embodiment 5（Compound carbon particle）, as described above, being with ozone, the negative pole of embodiment 3 to be lived The surface of property material is processed, and increased the material of oxygen content.Embodiment 5 negative electrode active material differential thermal thermogravimetric simultaneously Measure（TG-DTA）In result, occur in that the oxidation peak from clad respectively at 530 DEG C～550 DEG C, 750 DEG C～770 Occur in that the oxidation peak from graphite nuclear material at DEG C, and be 0.1 matter with the weight decrement of clad oxidation reaction Amount %.It follows that compared with the measurement result of the negative electrode active material gained for embodiment 3, peak temperature is all to low temperature sidesway Dynamic.Its reason can be estimated as, and the oxygen content due to clad in embodiment 5 increased compared with Example 3, is therefore easier Oxidation.And it is believed that for oxygen reactivity higher it is easier to occur clad within carbon oxidation reaction.Additionally, Although coating layer reduces because ozone processes, in compound carbon particle, the containing ratio of low-crystalline carbon is shown as 0.1 mass %～20 Quality %.
（5）The evaluation of embodiment 6
Negative electrode active material in embodiment 6（Compound carbon particle）Differential thermal thermogravimetric measure simultaneously（TG-DTA）In result, Obtain the oxidation peak from clad in 500 DEG C～520 DEG C of low temperature sides, come in 760 DEG C～780 DEG C of high temperature sides Oxidation peak from graphite nuclear material.Weight decrement with clad oxidation reaction is 20 mass %, meets the spy of the present invention Levy.
（5）The surface analyses of negative electrode active material used in embodiment 2～6
Then, by x-ray photoelectron optical spectroscopy（XPS）Carry out negative electrode active material used in embodiment 2,3,4,5,6 Matter（Compound carbon particle）Surface analyses.The results are shown in table 1.In this mensure, micro in air in order to remove Polluter, has carried out argon etching before the assay in advance.Negative electrode active material is placed on x-ray photoelectron light splitting（XPS）Dress After putting, fully carry out vacuum exhaust, and carry out argon ion etching under a high vacuum.Set ion current and etching period, from And make etch quantity（Depth）2nm is scaled with silicon dioxide.Then, the xps energy spectrum carrying out C1s and O1s measures.
Ownership from the chemical bond state of the xps energy spectrum of C1s is carried out as follows.C-O or C-OH key 286.3 ± The peak position of 0.3eV scope, in the peak position of 285.1 ± 0.3eV scope, C-C key is in 284.3 ± 0.3eV scope for c h bond Peak position, carries out the curve matching of power spectrum respectively, calculates the ratio of each key（atom%）.Similarly, from the change of the XPS of O1s The ownership learning bonded state is carried out as follows.That is, C-O key is in the peak position of 533.6 ± 0.3eV scope, C-OH key exists The peak position of 532.3 ± 0.3eV scope, C=O key, in the peak position of 531.2 ± 0.3eV scope, carries out the curve of power spectrum respectively Matching, calculates the ratio of each key（atom%）.
First, the negative electrode active material surface of embodiment 2（Clad）Concentration of carbon（Atomic percentage）For 97.9atom%, oxygen concentration is 2.1atom%.According to the XPS analysis of C1s, the carbon phase of C-O or C-OH state is for total carbon bag Containing 4atom%, most carbon is in C-C or c h bond state, wherein, C-C bonded state be total carbon 70atom%～ 80atom%.In the case of embodiment 3,4,5, the state of carbon similarly, does not observe significant difference.
Then, the XPS analysis result according to O1s, the chemical species containing aerobic is attributed to C=O, C-OH and C-O.Understand, On the surface of the negative electrode active material of embodiment 2, wherein C-OH and C-O is main constituent, and also includes belonging to C=O's The chemical species of high oxidation number state.Respective have ratio and be, C=O is 12atom%, and C-OH is 40atom%, and C-O For 48atom%.Further, since the evaluated error of this analysis has about ± 3atom%, it is taken as that C=O measures as total oxygen demand The scope of 9atom%～15atom%.
The negative electrode active material surface of embodiment 3（Clad）Concentration of carbon（Atomic percentage）For 97.8atom%, oxygen is dense Spend for 2.2atom%.Additionally, from the XPS analysis result of O1s, on the negative electrode active material surface of embodiment 3, C-OH It is main constituent with C-O, and also there are the C=O of high oxidation number state.
The negative electrode active material surface of embodiment 4（Clad）Concentration of carbon（Atomic percentage）For 97.1atom%, oxygen is dense Spend for 2.9atom%.Additionally, from the XPS analysis result of O1s, on the negative electrode active material surface of embodiment 4, C-OH It is main constituent with C-O, and also there are the C=O of high oxidation number state.
The negative electrode active material surface of embodiment 5（Clad）Concentration of carbon（Atomic percentage）For 95.7atom%, oxygen is dense Spend for 4.3atom%.From the XPS analysis result of O1s, on the negative electrode active material surface of embodiment 5, C=O, C-OH and The basic equivalent of C-O exists.Particularly on the surface of the negative electrode active material of embodiment 5, the 36atom%'s containing total oxygen demand The C=O of high oxidation number state.Evaluated error in view of this analysis has when about ± 3% it is believed that the negative pole in embodiment 5 is lived On the surface of property material, C=O measures the scope of the 33atom%～39atom% for total oxygen demand.
Finally, the negative electrode active material surface of embodiment 6（Clad）Concentration of carbon（Atomic percentage）For 97.5atom%, oxygen concentration is 2.5atom%.Additionally, from the XPS analysis result of O1s, in the negative electrode active material of embodiment 6 On matter surface, C-OH and C-O is main constituent, and also there are the C=O of high oxidation number state.
It is compared the XPS analysis of the graphite nuclear material of example 1.Although the oxygen concentration of graphite nuclei material surface and embodiment 2 ～4 negative electrode active material surface is essentially identical, but is with the marked difference on the negative electrode active material surface of embodiment 2～6 Do not observe the C=O this point of high oxidation number state.
In the known negative electrode active material in embodiment 2,3,4,5,6, the oxygen-containing carbon-coating shown in table 1 is formed as clad On the surface of graphite nuclear material.Estimate this clad closely sealed with internal graphite nuclear material, and the oxygen for Fig. 2 and Fig. 3 Change response characteristic and create some impacts.Its impact and effect are as described below.
The oxidation peak of the high temperature side shown in Fig. 2 and Fig. 3, depending on negative electrode active material of the present invention（Compound carbon particle）Stone The oxidation reaction of black nuclear material.The temperature of this oxidation reaction moves to than conventional graphite monomer oxidation peak（For example, Japanese Unexamined Patent Publication Oxidation peak near about 900 DEG C of Fig. 1 that 2001-229914 publication is recorded）Low low temperature side.It is contemplated that in Fig. 2 and In the test of Fig. 3, can estimate when the low-crystalline oxidation of coal of clad decomposes, this is reacted to the reaction of graphite nuclei material oxidation Starting point, promote the graphite nuclear material oxidation reaction of itself.Therefore, the high temperature side peak of the negative electrode active material of the present invention moves to Low temperature side, implys that the clad that formed by low-crystalline carbon to the adaptation of graphite nuclei material surface and uniformity（Pay I ま わ り, Throwing Power）Excellent that is to say, that clad uniformly and has densely coated graphite nuclei material list Face.But, the present invention is not restricted to this theory.
As shown in the above-mentioned character of the negative electrode active material of embodiment 2～embodiment 6, in the present invention, by changing Heat treatment condition during clad is formed on graphite nuclear material, can make to have C=O, C-OH and C-O on the surface of clad Functional group, and make the oxygen atom containing ratio of aforementioned functional groups in clad in the carbon atom of clad and the total amount of oxygen atom For being equivalent to the amount of 2atom%～5atom% oxygen.Particularly on the surface of clad during the state of formation high oxidation number, also Be in the xps energy spectrum say O1s ownership C=O oxygen amount, with respect to clad total oxygen demand it is desirable to be 7atom%～39atom%. This negative electrode active material is the material with following characteristics, i.e. differential thermal thermogravimetric in an atmosphere in algoscopy, is at least divided simultaneously Not 350 DEG C more but less than 600 DEG C within the temperature range of and less than more than 600 DEG C 850 DEG C of temperature within the scope of have at least 1 There is the oxidation peak at peak and in minimum temperature in maximum temperature in individual oxidation peak, and less than 850 DEG C of scope more than 350 DEG C The peak temperature difference with the oxidation peak at peak is less than 300 DEG C.Known will meet the negative electrode active material of such essential condition During for lithium ion battery, it is effective for the preservation characteristics of battery, the raising of cycle life.With regard to detailed examination Test result, be described below.
Here it is contemplated that adaptation by increasing clad and graphite nuclei material surface, with clad uniformly and Densely coated graphite nuclear material surface, thus prevent electrolyte and graphite nuclei material surface directly contact.As a result, due to electrolysis Liquid is difficult to reach the end of highly active graphite nuclear material（The end of graphene-structured）, therefore estimate and can suppress going back of electrolyte Former reaction, is favorably improved battery behavior.
More than, for the negative electrode active material of embodiment 2～6（Compound carbon particle）For, by low-crystalline carbon coating layer The atomic ratio of the carbon of the functional group on surface and oxygen, C1s analysis result and O1s analysis result are shown in table 1.In addition, the C1s of table 1 divides Numerical value shown in analysis result and O1s analysis result hurdle represents respective key ratio（atom%）.The negative electrode active of embodiment 2～6 Material（Compound carbon particle）A big feature of clad be to comprise the functional group containing C=O key, and the ratio of C-OH and C=O Rate, in terms of the atomic composition ratio of oxygen in each functional group, is 1：1～4：1.
[table 1]
Using above-mentioned negative electrode active material（Compound carbon particle）Manufacture during negative pole it is necessary to there be high speed charge-discharge characteristic. At this moment, conductive auxiliary agent can be added in negative pole.Conductive auxiliary agent is due to being not related to absorption and the releasing of lithium ion, but conduct electricity The medium of son works, and the therefore absorption on lithium ion in negative electrode active material and releasing reaction does not affect.
In addition it is also possible to add the electric conductivity comprising polyacene, polyparaphenylene, polyaniline, polyacetylene in aforementioned negative pole Macromolecular material and use.
It is in embodiment 2～6, because negative electrode active material is powder, therefore that negative electrode binder is mixed, And bonded on collector while so that powder is bonded to each other.In the present invention it is desirable to make negative pole in aforementioned negative pole live The particle diameter of property material is below the thickness of the mixture layer comprising negative electrode active material and negative electrode binder.When in negative electrode active material There are when there is the coarse grain of aforementioned mixture layer thickness dimensions above, preferably remove beforehand through sieve classification, air classification etc. Coarse grain, and using the particle below aforementioned mixture layer thickness.
Copper Foil that collector can be 10 μm～100 μm using thickness, thickness are 10 μm～100 μm, aperture be 0.1mm～ The copper perforated foil of 10mm, expansion alloy, foamable metal sheet etc., its material apart from copper, can also using rustless steel, titanium, Nickel etc..In the present invention, material, shape, manufacture method etc. do not limit, it is possible to use arbitrary collector.
Make to be mixed with negative electrode active material, aforementioned negative electrode binder by doctor blade method, infusion process, nebulization etc. and fit When the cathode size of solvent is attached on collector, then solvent is dried, and extrusion forming is carried out to negative pole by roll-in, thus Make aforementioned negative pole.
<Electrochemical evaluation 1>
Using the negative electrode active material shown in table 1（Compound carbon particle）, it is to be to electrode, with Li metal that group is filled with Li metal The electrochemical cell of reference electrode.The battery of the negative electrode active material using embodiment 2 is designated as C1, by using embodiment 3 The battery of negative electrode active material is designated as C2, and the battery of the negative electrode active material using embodiment 4 is designated as C3, will be using embodiment The battery of 5 negative electrode active material is designated as C4, and the battery of the negative electrode active material using embodiment 6 is designated as C5, will use than It is designated as C6 compared with the battery of the negative electrode active material of example 1.In each negative electrode active material of 95 mass parts, mixing 5 mass parts are as negative The PVDF of very viscous mixture, and the METHYLPYRROLIDONE adding as solvent makes the negative electrode active material in cathode size The solid component concentration being combined with PVDF is 55 mass %.Fully kneaded using planetary mixer, and by doctor blade method by institute The cathode size obtaining is coated on the Copper Foil collector surface that thickness is 10 μm.Using the drying oven of 120 DEG C, air atmosphere, After METHYLPYRROLIDONE is dried, carry out extrusion forming using roll squeezer, make each negative pole.Cathode agent density is 1.5g/cm3.Dividing plate uses and has been laminated polyethylene and polyacrylic micro- porous plate（Thickness is 25 μm）.Electrolyte is using dissolving 1M LiPF6The electrolyte comprising ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate.In addition, the volume ratio of each solvent Rate is 1：1：1.
In 0.1mA/cm2Electric current density（Correspond approximately to the electric current density of 8 hour rates）Under, with lower voltage limit as 10mV, The maximum charge time is that the condition of 8 hours is charged to above-mentioned 6 kinds of batteries, after being then passed through the dwell time of 30 minutes, enters Row determines electric current density（0.1mA/cm2）Electric discharge until upper voltage limit 1V.Again after 30 minutes dwell times, repeat on The charge-discharge cycles stated.
Table 2 represent " initial discharge capacity " and by primary charging capacity with " irreversible calculated by the difference of discharge capacity Capacity " result.In addition, each capacity is calculated with the per unit mass of negative electrode active material used.Understand, employ this The battery of negative electrode active material in bright embodiment（C1～C5）, with respect to the battery employing negative electrode active material in comparative example 1 For C6, irreversible capacity is little, and the discharge capacity at initial stage is also big.
<Electrochemical evaluation 2>
Negative electrode active material using the embodiment 2～6 shown in table 1（Compound carbon particle）, make the cylinder type electricity of Fig. 1 Pond, carries out battery behavior evaluation test.The battery employing the negative electrode active material of the embodiment 2 shown in table 1 is designated as B1, will The battery employing the negative electrode active material of embodiment 3 is designated as B2, and the battery employing the negative electrode active material of embodiment 4 is remembered For B3, the battery employing the negative electrode active material of embodiment 5 is designated as B4, the negative electrode active material of embodiment 6 will be employed Battery be designated as B5, the battery employing the negative electrode active material of comparative example 1 is designated as B6.In each negative electrode active material of 95 mass parts In matter, mixing 5 mass parts are as the PVDF of negative electrode binder, and the METHYLPYRROLIDONE adding as solvent makes to bear The solid component concentration that negative electrode active material in the slurry of pole and PVDF are combined is 55 mass %.Filled using planetary mixer Divide mixing, and by doctor blade method, the cathode size of gained is coated on the Copper Foil collector surface that thickness is 10 μm.Using 120 DEG C, the drying oven of air atmosphere, after METHYLPYRROLIDONE is dried, carry out extrusion forming using roll squeezer, make Each negative pole.
Each battery（B1～B6）In positive active material used be LiNi1/3Mn1/3Co1/3O2.Mix 89 mass parts this just Pole active substance, 4 mass parts acetylene blacks and 7 mass parts are as the PVDF of positive electrode binder, and add N- methyl -2- pyrroles Alkanone, modulates anode sizing agent.The decentralized processing of material, using known kneading machine, dispersion machine.Often single with regard to positive active material Quality, the thickness of positive pole and density that plane amasss, each battery is all identical condition.
As dividing plate, using being laminated polyethylene and polyacrylic micro- porous plate（Thickness is 25 μm）.
As electrolyte, using having dissolved 1M LiPF6Comprise ethylene carbonate, dimethyl carbonate and carbonic acid ethyl first The electrolyte of ester.In addition, the volume ratio of each solvent is 1：1：1.
Each battery is made to flow through the current value being equivalent to 1 hour rate（15A）Charging current, and carried out with the voltage of determining of 4.2V Charge within 1 hour.Then, flow through the discharge current of 15A, be discharged to cell voltage and reach 3.0V.Again under the same conditions, continue Carry out 100 charge and discharge cycles, obtained through 100 with respect to the ratio of initial discharge capacity by the discharge capacity of the 100th circulation Capacity sustainment rate during secondary circulation.The results are shown in " capacity sustainment rate when 100 circulations of table 2（%）" hurdle.
Above measurement result is summarized in table 2.Understand, the battery in the embodiment of the present invention（B1～B5）Electricity with comparative example Pond（B6）Compare, be also excellent in terms of capacity sustainment rate when through 100 circulations.
[table 2]
<Electrochemical evaluation 3>
The cylindrical shape lithium ion battery of 8 Fig. 1 is connected in series, is assembled into the set of cells of Fig. 4（Battery module）401, and It is assembled in the power-supply system of Fig. 4.Lithium ion battery is made battery in above-mentioned electrochemical evaluation 2.This electric power storage system System can serve as moving body accumulating system or fixed accumulating system.
In addition, in the diagram, 401 expression set of cells, 402 expression lithium ion batteries（Monocell）, 403 expression positive terminals, 404 expression buses, 405 expression battery cans, 406 expression support members, 407 expression positive pole outside terminals, 408 expression negative outer Terminal, 409 represent calculation processing unit, 410 expression charge-discharge circuits, 411 expression external equipments, 412 expression electric lines of force, 413 tables Show holding wire, 414 expression external power cables.
Cylindrical shape lithium ion battery（Hereinafter simply referred to as " battery "）402, fixing by support member 406.Each battery is handed over For the direction changing positive terminal 403 and battery can 405, and it is connected in series by bus 404.In addition, in the diagram, positive terminal Son 403 and battery can 405 are respectively equivalent to the battery cover 120 of Fig. 1 and the battery can 113 of Fig. 1.8 batteries 402 being connected in series End, be connected with positive pole outside terminal 407 and negative outer terminal 408.In addition, being connected in series 8 electricity in set of cells 401 Pond 402, but the number of battery 402 connecting is not limited to 8, as long as more than 2 it is possible to according to set of cells 401 Size suitably sets.Additionally, the type of attachment of battery 402 is not limited to this in set of cells 401, can be in parallel it is also possible to It is connection in series-parallel.
Positive pole outside terminal 407 and negative outer terminal 408, are charged with enforcement set of cells 401 by electric lines of force 412 and put The charge-discharge circuit 410 of electricity connects.The action of charge-discharge circuit 410, by holding wire 413, is controlled by calculation processing unit 409. Calculation processing unit 409, in addition to the electric current and voltage of control charge-discharge circuit 410, also controls by the outside of set of cells 401 Terminal（Positive pole outside terminal 407, negative outer terminal 408）Flow to electricity during discharge current and the electric discharge between external equipment 411 Pressure.During set of cells 401 electric discharge, electric power is supplied to external equipment 411 by external power cable 414.
In this evaluation, the composition of negative electrode active material is the negative electrode active material to 95 mass parts embodiments 4（Compound carbon granules Son）In with the addition of 5 mass parts as the composition of the PVDF of negative electrode binder.Positive active material is LiNi1/3Mn1/3Co1/3O2. For other compositions, and the composition described in above-mentioned electrochemical evaluation 2 is same.
Further, since this evaluation is the test for confirming effectiveness of the present invention, therefore the outside for power consumption is being installed Equipment（For example, electronics load device, motor）Place, employs as the external equipment having power supply and power consumption two aspect function concurrently 411 supply load power supply.Using this supply load power supply, and the electric vehicles such as electric automobile, work equipment, or dispersion Type electric power storage system, standby power system etc. actually used when compare, difference will not be brought to effect of the present invention.
At once the charge test carrying out after the system assembling, is and to be born from charge-discharge circuit 410 to positive pole outside terminal 407 Pole outside terminal 408 flows through the current value being equivalent to 1 hour rate（15A）Charging current, and carry out 1 with the voltage of determining of 33.6V Hour charges.Set determines magnitude of voltage herein, is 8 times that determine magnitude of voltage 4.2V of aforementioned monocell of value.Battery set charge/discharge Required electric power is by supply load device（External equipment 411）Supply.
Discharge test be flow through from positive pole outside terminal 407 and negative outer terminal 408 to charge-discharge circuit 410 reverse Electric current, and by the supply load device consumption electric power as external equipment 411.Discharge current is set to the condition of 0.5 hour rate（Make For discharge current, it is 7.5A）, it is discharged to positive pole outside terminal 407 and the voltage between terminals of negative outer terminal 408 reach 24V.
Under this discharge and recharge experimental condition, obtain charging capacity be 15.0Ah, discharge capacity be 14.95Ah primary Energy.Additionally, in the charge and discharge cycles test implementing 1000 circulations, having obtained 92% capacity sustainment rate.In addition, will use The system of the negative electrode active material of embodiment 4 is designated as S1.
In the structure of Fig. 4, respectively negative electrode active material is changed into negative electrode active material and the ratio of the embodiment 5 of table 1 Negative electrode active material, manufacturing system S2 and S3 compared with example 1.For each system, with same as before under conditions of implement 1000 The charge and discharge cycles test of secondary circulation.As a result, the capacity sustainment rate for 89%, S3 for the capacity sustainment rate of S2 is 73%.
It follows that the negative electrode active material of the embodiment of the present invention 4 and embodiment 5, follow for improving lithium ion battery Ring property is effective.
Then, to above-mentioned 3 kinds of systems, reach charged state under the same conditions, and under 50 DEG C of ambient temperature, place 30 days.Then, re-start charge and discharge cycles test after discharge, measure the discharge capacity of the 10th circulation, as 50 DEG C place after capacity sustainment rate.In addition, capacity sustainment rate, it is with the initial capacity before 50 DEG C of placements for 100%, and as phase The value that the ratio of this value is obtained.This result of the test is that S1 is 93%, S2 is 75% for 92%, S3, it follows that the present invention Embodiment 4 and the negative electrode active material of embodiment 5, are also effective for 50 DEG C of preservation characteristics.
Based on content described above, show the concrete application example of the system, and understand the effect of the present invention.In addition, Do not changing in the range of present subject matter, thus it is possible to vary specific constituent material, part etc..As long as additionally, comprising the present invention Element, then can also add known technology, or be replaced with known technology.
The lithium ion battery of the present invention and battery module, except for mobile electronic apparatus, portable phone, electric tool Beyond people's livelihood articles for use, can be also used for electric automobile, the storage accumulator of regenerative resource, pilotless automobile, nurse The power supply of equipment etc..Additionally, the lithium ion battery of the present invention, can be applicable to visit for the universe exploring the moon, Mars etc. The power supply of rope airship.Further, it is also possible to for the building on space station, the earth or other celestial body or living space（No By airtight or open state.）, mobile spacecraft, planet aircraft between planet（land rover）, in water or marine The purifications of the air adjustment in various spaces, temperature adjustment, sewage or air such as confined space, submarine, Fish observation equipment, The various power supplys of power etc..
According to the present invention it is possible to provide a kind of lithium ion battery that improve cycle life and High temperature storage characteristic.
Industrial applicibility
Present invention can be suitably applied to the lithium ion batteries such as lithium rechargeable battery, the moving body electric power storage system using this battery System or fixed accumulating system etc..
Japanese patent application laid filed in September in 2010 24 days is willing to the disclosure of No. 2010-213866, and its entirety is logical Cross with reference to and be introduced in this specification.
Whole documents described in this specification, patent application and technical standard, each with specifically and respectively describing Individual document, patent application and technical standard by referring to and situation about being introduced into equally quote to this specification.

Claims (19)

1. a kind of lithium ion battery, it contains the negative pole comprising to adsorb and release the negative electrode active material of lithium, positive pole, non- Water-Electrolyte and nonaqueous solvent, described negative electrode active material is the cladding on the surface of graphite nuclear material with low-crystalline carbon The compound carbon particle of layer, described clad has C=O, C-OH and C-O functional group, the carbon atom of described clad and oxygen Oxygen atom containing ratio in the total amount of atom is 2atom%～5atom%, in aerial thermogravimetric algoscopy, described negative pole Active substance respectively 350 DEG C more but less than 600 DEG C within the temperature range of and more than 600 DEG C 850 DEG C below temperature range Inside there is the oxidation peak in maximum temperature at least one oxidation peak, and less than 850 DEG C of scope more than 350 DEG C with peak Poor with the peak temperature of the oxidation peak in minimum temperature with peak be less than 300 DEG C.
2. lithium ion battery as claimed in claim 1, in described clad, the oxygen containing ratio of C=O, total in described clad It is 7atom%～39atom% in oxygen amount.
3. lithium ion battery as claimed in claim 1 or 2, the low-crystalline carbon of described clad is amorphous carbon.
4. lithium ion battery as claimed in claim 1, the ratio of C-OH and C=O in described clad, with each functional group The atomic composition ratio of oxygen is calculated as 1：1～4：1.
5. lithium ion battery as claimed in claim 1, described negative electrode active material passes through calculated by X-ray diffraction method (002) face interval d002For 0.3354nm～0.3370nm, crystallite dimension Lc is 20nm～90nm.
6. lithium ion battery as claimed in claim 1, the thickness of described clad is 10nm～100nm.
7. lithium ion battery as claimed in claim 1, strength ratio I of the Raman peaks of described negative electrode active material1360/I1580For 0.1～0.7.
8. lithium ion battery as claimed in claim 1, the irreversible capacity of described negative electrode active material unit mass is 20mAh/g～31mAh/g, and the discharge capacity density of described negative electrode active material is 350mA/g～365mA/g.
9. lithium ion battery as claimed in claim 1, described graphite nuclear material is the stone having carried out isotropism pressurized treatments Black particle.
10. lithium ion battery as claimed in claim 1, described clad is by making organic compound or its mixture non- The carbon coating being thermally decomposed in oxidizing atmosphere and being formed on the surface of described graphite nuclear material by described low-crystalline carbon.
11. lithium ion batteries as claimed in claim 10, described clad is by organising described under the contacting conditions Compound or the carbon coating of its mixture and described graphite nuclei material thermal decomposition gained.
12. lithium ion batteries as described in claim 10 or 11, described organic compound is the organic high score with liquid phase carbonation Sub- compound.
13. lithium ion batteries as described in claim 10 or 11, described organic compound is with the organic resin of solid phase carbonization.
14. lithium ion batteries as claimed in claim 1, containing ratio in described compound carbon particle for the described low-crystalline carbon is 0.1 mass %～20 mass % of total quality of described graphite nuclear material and described low-crystalline carbon.
15. lithium ion batteries as claimed in claim 1, described positive pole comprises positive active material, conductive auxiliary agent, positive pole bonding Agent and collector.
16. lithium ion batteries as claimed in claim 1, described positive pole comprises positive active material, conductive auxiliary agent, positive pole bonding Agent and collector, this positive active material is selected from LiCoO2、LiNiO2、LiMn2O4、LiMnO3、LiMn2O3、LiMnO2、 Li4Mn5O12、LiMn2-xMxO2、Li2Mn3MO8、Li1-xAxMn2O4、LiNi1-xMxO2、LiFeO2、Fe2(SO4)3、LiCo1-xMxO2、 LiNi1-xMxO2、Fe(MoO4)3、FeF3、LiFePO4And LiMnPO4At least one in the group being formed, wherein, described LiMn2-xMxO2In, M=Co, Ni, Fe, Cr, Zn or Ta, x=0.01～0.2；Described Li2Mn3MO8In, M=Fe, Co, Ni, Cu Or Zn；Described Li1-xAxMn2O4In, A=Mg, B, Al, Fe, Co, Ni, Cr, Zn or Ca, x=0.01～0.1；Described LiNi1- xMxO2In, M=Co, Fe or Ga, x=0.01～0.2；Described LiCo1-xMxO2In, M=Ni, Fe or Mn, x=0.01～0.2；Institute State LiNi1-xMxO2In, M=Mn, Fe, Co, Al, Ga, Ca or Mg, x=0.01～0.2.
17. lithium ion batteries as claimed in claim 1, described positive pole comprises positive active material, conductive auxiliary agent, positive pole bonding Agent and collector, this positive active material is LiNi1/3Mn1/3Co1/3O2.
A kind of 18. battery modules, by the lithium ion battery any one of more than 2 claim 1～17 with series, parallel Or connection in series-parallel form is formed by connecting.
A kind of 19. moving body accumulating systems or fixed accumulating system, by outside terminal by the electricity described in claim 18 Pond module is connected in the charge-discharge circuit being connected with external equipment and forms.
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