CN105940530B - Lithium ion secondary battery positive electrode slurry, the anode obtained using the slurry and its manufacturing method, using lithium ion secondary battery obtained by the anode and its manufacturing method - Google Patents

Lithium ion secondary battery positive electrode slurry, the anode obtained using the slurry and its manufacturing method, using lithium ion secondary battery obtained by the anode and its manufacturing method Download PDF

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CN105940530B
CN105940530B CN201580006248.1A CN201580006248A CN105940530B CN 105940530 B CN105940530 B CN 105940530B CN 201580006248 A CN201580006248 A CN 201580006248A CN 105940530 B CN105940530 B CN 105940530B
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lithium ion
secondary battery
ion secondary
acid
slurry
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CN105940530A (en
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青木优介
花崎充
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Lishennoco Co ltd
Resonac Holdings Corp
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Showa Denko KK
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention provides a kind of lithium ion secondary battery positive electrode slurry, it contains: (A) positive active material, (B) conductive auxiliary agent, (C) resin binder comprising at least one of ethylenically unsaturated carboxylic acids ester and ethylenically unsaturated carboxylic acids with the copolymer of aromatic ethenyl compound, (D) dispersing agent is viscosified, (E) pH regulator and (F) water, 100 mass parts of solid component relative to positive active material, the content of (E) the pH regulator is 0.1 mass parts or more and 1.0 below the mass, the pH of slurry is 6.0~8.0 at 23 DEG C.

Description

Lithium ion secondary battery positive electrode slurry, the anode obtained using the slurry and its system Make method, using lithium ion secondary battery obtained by the anode and its manufacturing method
Technical field
The anode and its manufacturing method that are obtained the present invention relates to lithium ion secondary battery positive electrode slurry, using the slurry, Use lithium ion secondary battery obtained by the anode and its manufacturing method.
Background technique
Lithium ion secondary battery is widely used as power supply or the electric power storage of the portable devices such as mobile phone, laptop Hiding use or electric car etc. require the driving power of the industry device of high life.From now on, people's livelihood equipment requirement lightweight or Miniaturization, it is desirable that the battery with higher energy density.In addition, being stored in industry equipment along with electric car or fixed The further of electric equipment is popularized, it is desirable that high output, large capacity, long-life performance corresponding to large-sized battery.
As the means for realizing the high-energy density of lithium ion secondary battery, high output, large capacity, long lifetime, mention The operating voltage of high anode, the method for realizing the high capacity of battery are concerned.For example, on the basis of lithium can with 4.3V with On high voltage steadily store, release lithium and electronics with LiMO2The transition metal containing lithium that (M is transition metal) indicates The exploitation as a positive electrode active material such as oxide is carrying out.
In addition, the anode for lithium ion secondary battery usually has the knot that positive active material is stacked on to aluminium collector Structure other than positive active material, is also used for positive active material to be bonded to each other and incite somebody to action in positive electrode active material layer The positive active material bonding agent Nian Jie with collector.In order to realize high capacity, the long lifetime of lithium ion secondary battery, as Bonding agent, it is desirable that with less amount and the high material of bonding force.
In general, lithium ion secondary battery positive electrode is coated on collector come when manufacturing anode, as slurry with slurry Adhesive, be most widely used that using the N-Methyl pyrrolidone (hereinafter also referred to " NMP ") using organic solvent system as The polyvinylidene fluoride (hereinafter also referred to " PVDF ") of solvent.
But PVDF system adhesive cannot by positive active material each other and active material is be bonded well with collector, The problem of having the charge/discharge cycle characteristics of lithium ion secondary battery reduces.In actual use, in order to ensure positive electrode active material Matter sufficient cementability to each other and between active material and collector, needs a large amount of PVDF adhesive, the result is that lithium ion The capacity of secondary cell can reduce.Moreover, the manufacture of PVDF system adhesive is because nmp solvent has the reason of mutagenicity etc., thus Carrying capacity of environment is high, is conceived to the exploitation for using water as the new adhesive of solvent.
On the other hand, in the exploitation of positive aqueous adhesive, it is widely used as the benzene of cathode aqueous adhesive Ethylene-butadiene rubber (hereinafter also referred to " SBR ") is concerned.In addition, by aqueous solvent and be used as thickening dispersion The carboxymethyl cellulose (hereinafter also referred to " CMC ") of agent, can carry out the low manufacture of carrying capacity of environment, and realize positive active material that Good cementability around here and between active material and collector.
But can to enumerate inoxidizability low for feature of SBR adhesive its construction.The repeated charge under high voltage condition, It is required that the utilization of SBR adhesive may make the long-life characteristics of battery in the anode of antioxidative lithium ion secondary battery It reduces.
And, it is however generally that the reactivity of water and lithium compound is very high, and the transition metal oxide containing lithium is utilized Positive active material be noted the stage for manufacturing positive slurry it is easy reacted with water, and imply that because of the reaction, from And lithium can be detached from out of anode, can incur reduction or the high resistance of battery capacity.Therefore, opening in anode aqueous adhesive In hair, discovery inhibits the positive active material in slurry to be important with the method for water reacted.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 10-255808 bulletin
Patent document 2: Japanese Unexamined Patent Publication 10-241693 bulletin
Problems to be solved by the invention
The object of the present invention is to provide a kind of water-based lithium ion secondary battery positive electrode slurries, are obtained using the slurry The anode and its manufacturing method arrived, using lithium ion secondary battery obtained by the anode and its manufacturing method, which is that can press down Positive active material processed is reacted with water, it is possible to provide has both high capacity characteristics, low resistance characteristic and high charge-discharge circulation sustainment rate The lithium ion secondary battery of characteristic.
Means for solving the problems
That is, system of the present invention is indicated by following (1)~(10).
[1] a kind of lithium ion secondary battery positive electrode slurry, which is characterized in that led containing (A) positive active material, (B) Electric auxiliary agent, (C) resin binder, (D) thickening dispersing agent, (E) pH regulator and (F) water, under (C) resin binder includes Copolymer is stated, the copolymer is at least one of ethylenically unsaturated carboxylic acids ester and ethylenically unsaturated carboxylic acids and aromatic vinyl The copolymer of based compound, relative to 100 mass parts of solid component of positive active material, the content of (E) the pH regulator For more than 0.1 mass parts and 1.0 below the mass, the pH of slurry is 6.0~8.0 at 23 DEG C.
[2] the lithium ion secondary battery positive electrode slurry according to [1], wherein (E) the pH regulator be selected from comprising The compound of organic acid, inorganic acid, the organic acid are selected from following compound, and the compound contains 1 independent or compoundly At least one of above carboxyl, sulfo group and phosphonic acid base group, the inorganic acid in phosphoric acid, boric acid and carbonic acid at least 1 kind.
[3] the lithium ion secondary battery positive electrode slurry according to [1] or [2], wherein (E) the pH regulator is It is at least one kind of in 1,2,3,4- butane tetracarboxylic acid, citric acid, succinic acid, acetic acid, methanesulfonic acid, propane sulfonic acid, carbonic acid.
[4] the lithium ion secondary battery positive electrode slurry according to [1] or [2], wherein (E) the pH regulator is The pH additive of alkalinity, alkaline pH is selected from the pH additive of organic basic with additive, the pH of inorganic alkaline is added Agent, the pH additive of organic basic are selected from least one of primary amine, secondary amine, tertiary amine and quaternary ammonium, and the pH of inorganic alkaline is used Additive is selected from least one of ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide.
[5] the lithium ion secondary battery positive electrode slurry according to any one of [1]~[4], wherein relative to anode 100 mass parts of solid component of active material, containing it is more than 0.2 mass parts and 5.0 below the mass described in (C) resin-bonding Agent.
[6] the lithium ion secondary battery positive electrode slurry according to any one of [1]~[5], wherein (D) increases Viscous dispersing agent contains more than one following water soluble polymers, and the water soluble polymer includes carboxymethyl cellulose, polycyclic Oxidative ethane, polyacrylic acid, poly-N-vinyl acetamide and acrylic acid and N- vinyl acetamide copolymer.
[7] a kind of lithium ion secondary battery anode is using the electricity of lithium ion secondary described in any one of [1]~[6] Obtained from the anode slurry of pond.
[8] a kind of manufacturing method of lithium ion secondary battery anode, the lithium ion secondary battery anode is in anode Has the positive electrode active material layer containing positive active material on collector, the manufacturing method has to the positive electrode collector Lithium ion secondary battery positive electrode described in any one of upper supply [1]~[6] forms the positive electrode active material layer with slurry Process.
[9] a kind of lithium ion secondary battery is using obtained from lithium ion secondary battery anode described in [7].
[10] a kind of manufacturing method of lithium ion secondary battery, it is with the following process: any one of preparation [1]~[6] institute The process for the lithium ion secondary battery positive electrode slurry stated；The lithium ion secondary battery positive electrode is coated on positive collection with slurry Electric body and the process for forming positive electrode active material layer to manufacture lithium ion secondary battery anode；And assembling have the lithium from The process of the lithium ion secondary battery of sub- anode of secondary cell.
Invention effect
According to the present invention, and with specific resin binder with specific dispersing agent is viscosified, and then will using pH regulator Neutral region of the pH control of aquo-lithium ion anode of secondary battery slurry 6.0~8.0, by using the aquo-lithium ion Anode of secondary battery slurry, it is possible to provide inhibit reacting for positive active material in positive slurry and water, have both Gao Rong The lithium ion secondary battery and its anode of flow characteristic, low resistance characteristic and high charge-discharge circulation sustainment rate characteristic.
Specific embodiment
Hereinafter, the present invention will be described in detail.
[lithium ion secondary battery positive electrode slurry]
Lithium ion secondary battery positive electrode slurry of the invention contains (A) positive active material, (B) conductive auxiliary agent, (C) tree Rouge adhesive, (D) thickening dispersing agent, (E) pH regulator and (F) water, (C) resin binder include following copolymers, institute Stating copolymer is at least one of ethylenically unsaturated carboxylic acids ester and ethylenically unsaturated carboxylic acids and aromatic ethenyl compound Copolymer, relative to 100 mass parts of solid component of positive active material, the content of (E) the pH regulator is 0.1 mass parts Above and 1.0 below the mass, the pH of slurry is 6.0~8.0 at 23 DEG C.
<(A) positive active material>
As a positive electrode active material, as long as can be used for the positive active material of lithium ion secondary battery, just without special It limits, cobalt acid lithium (LiCoO can be used2), spinel lithium manganate (LiMn2O4), olivine-type LiFePO4 (LiFePO4)、Ni- The nickeliferous lithium complex chemical compound such as Mn-Co system, Ni-Mn-Al system and Ni-Co-Al system, LiTiS2、LiMnO2、LiMoO3、LiV2O5Deng One of oxygen group compounds etc. or a variety of uses of combination.
<(B) conductive auxiliary agent>
As conductive auxiliary agent, as long as conductive substance, there is no particular limitation, generally preferably use carbon material. It as carbon material, is not particularly limited as long as conductive carbon material, particularly preferably uses graphite, carbon black, carbon fiber One of dimension etc. or a variety of uses of combination.
As carbon black, such as acetylene black, Ketjen black, furnace black, channel black and thermal black, preferably acetylene black, section's qin can be enumerated It is black.
As for the content of conductive auxiliary agent, relative to 100 mass parts of solid component of (A) ingredient, preferably 1 mass parts with It is upper, 10 below the mass, more than more preferably 2 mass parts, 8 below the mass, more than further preferably 4 mass parts, 6 mass Part or less.
<(C) resin binder>
Resin binder is at least one of ethylenically unsaturated carboxylic acids ester and ethylenically unsaturated carboxylic acids and aromatic vinyl The copolymer of based compound.
Relative to 100 mass parts of solid component of (A) positive active material, in terms of solid component containing 0.2 mass parts with Upper and 5.0 resin binder of the invention below the mass, preferably comprises 0.2 mass parts or more 3.0 below the mass.Pass through It is set as above range, it is good that cementability of the positive active material to each other and between positive active material and collector can be provided Positive slurry and anode, and then by utilizing the anode, it can provide with high initial discharge capacity and excellent high temperature The lithium ion secondary battery of charge/discharge cycle characteristics.Here, 100 mass parts of solid component relative to (A) positive active material, When resin binder is lower than 0.2 mass parts, the tendency that the cementability between active substance and collector reduces, more than 5.0 mass When part, have the tendency that the initial discharge capacity of lithium ion secondary battery reduces.
At least one of ethylenically unsaturated carboxylic acids ester and ethylenically unsaturated carboxylic acids are total to aromatic ethenyl compound Aromatic ethenyl compound in polymers is the compound with olefinic carbon-to-carbon double bond and aromatic rings.As aromatic vinyl Based compound can be enumerated such as styrene, α-methylstyrene, styrene sulfonic acid.It is excellent as aromatic ethenyl compound It is selected as styrene.
As ethylenically unsaturated carboxylic acids ester, such as α, β-unsaturated monocarboxylic acid or dicarboxylic acids (acrylic acid, methyl can be enumerated Acrylic acid, crotonic acid, Yi Kang acid, maleic acid, fumaric acid etc.) Arrcostab, the alkyl chain of ester be preferably carbon atom number 1~18, More preferably straight-chain, branched or the cricoid alkyl chain of carbon atom number 2~12, further preferably carbon atom number 2~8. As ethylenically unsaturated carboxylic acids ester, it is however preferred to have (the first of the straight-chain of carbon atom number 2~8, branched or cricoid alkyl chain Base) acrylate.In addition, (methyl) acrylic acid is methacrylic acid or acrylic acid.
If moreover, do not damage cementability of the positive active material to each other and between positive active material and collector, As at least one of the ethylenically unsaturated carboxylic acids ester of resin binder and ethylenically unsaturated carboxylic acids and aromatic ethenyl Following monomer can also be copolymerized in the copolymer of compound: (methyl) hydroxyalkyl acrylates, (methyl) acrylic-amino alkane It is base ester, (ethylene, propylene, butylene, different as the vinyl ester of representative, monoene hydro carbons using vinyl acetate or alkyl acid vinyl ester Butylene etc.), alkadienes (allene, methyl allene, butadiene), the olefinic containing carbonyl such as diacetone acrylamide it is unsaturated single Body, ethylenically unsaturated monomer containing sulfonic group.These monomers can be a variety of for a kind of or combination.
In above-mentioned resin binder, from point of the positive active material improved in lithium ion secondary battery positive electrode slurry From the perspective of dissipating property, and in order to improve the characteristic of lithium ion secondary battery, and from further increasing to the resistance to of electrolyte From the perspective of inoxidizability in stripping property and anode, resin binder is preferably that styrene-(methyl) acrylate is total Polymers, styrene-(methyl) acrylic copolymer or styrene-(methyl) acrylate-(methyl) acrylic copolymer, benzene Ethylene-(methyl) Acrylate-Acrylic-sodium styrene sulfonate copolymer, more preferably styrene-(methyl) acrylate- Acrylicstyrene sodium sulfonate copolymers.
It is closed relative at least one of ethylenically unsaturated carboxylic acids ester and ethylenically unsaturated carboxylic acids and aromatic vinyl 100 molar part of copolymer structure unit of object, the content of ethylenically unsaturated carboxylic acids ester units are preferably 25 molar parts or more and 85 Molar part is hereinafter, more than more preferably 30 molar parts and below 80 molar parts.By making containing for ethylenically unsaturated carboxylic acids ester units Amount within the above range, acquisition anode flexibility, heat resistance improve, and positive active material to each other and active material with Cementability between collector improves.
It is closed relative at least one of ethylenically unsaturated carboxylic acids ester and ethylenically unsaturated carboxylic acids and aromatic vinyl 100 molar part of copolymer structure unit of object, the content of ethylenically unsaturated carboxylic acids unit are preferably 1 molar part or more and 10 moles Part is hereinafter, more than more preferably 1 molar part and below 5 molar parts.By making the content of ethylenically unsaturated carboxylic acids monomeric unit exist In above range, can maintain the copolymer of aromatic ethenyl compound and ethylenically unsaturated carboxylic acids stability of emulsion polymerization or Mechanical stability, cementability of the positive active material to each other and between positive active material and collector improve.
In addition, in resin binder of the invention, especially ethylenically unsaturated carboxylic acids ester and ethylenically unsaturated carboxylic acids extremely The copolymer of few one and aromatic ethenyl compound as needed can also be by (methyl) acrylic acid as crosslinking agent The α containing epoxy group, β-olefinic unsaturated compound such as ethylene oxidic ester, vinyltriethoxysilane, γ-acryloxy third The α containing water-disintegrable alkoxysilyl, β-olefinic unsaturated compound such as base trimethoxy silane, ethylene glycol two (methyl) third Olefin(e) acid ester, trimethylolpropane tris (methyl) acrylate, (methyl) allyl acrylate, divinylbenzene, O-phthalic The monomers such as the polyfunctional vinyls compound such as diallyl phthalate import in the copolymer used as positive electrode binder, make itself It is cross-linked to each other or is crosslinked with the olefinic unsaturated compound of active hydrogen group at subassembly.Alternatively, it is also possible to contain The α of carbonyl, β-olefinic unsaturated compound etc. import in copolymer, can be with more hydrazine compounds, particularly careless acid dihydrazide, amber There is the compound combination of 2 or more hydrazide groups to be crosslinked for amber acid dihydrazide, adipic dihydrazide, polypropylene acid dihydrazide etc..
For obtaining resin binder of the invention, particularly for obtaining ethylenically unsaturated carboxylic acids ester and olefinic unsaturation Currently known method can be used in the polymerization of at least one of carboxylic acid and the copolymer of aromatic ethenyl compound, It is preferable to use emulsion polymerizations.The surfactant used when as emulsion polymerization can be used common anionic surface living Property agent, nonionic surfactant.As anionic surfactant, such as alkylbenzene sulfonate, alkyl sulfide can be enumerated Acid esters salt, polyethylene oxide alkyl ethers sulfuric acid, fatty acid salt etc. can enumerate polycyclic as nonionic surfactant Oxidative ethane alkyl ether, polyethylene oxide alkyl phenyl ether, the polycyclic phenyl ether of polyethylene oxide, polyoxyalkylene alkyl ether, sorb Sugar alcohol acid anhydride aliphatic ester, polyoxyethylene sorbitan aliphatic ester etc..A kind of or combination can be used in these surfactants A variety of uses.
The usage amount of surfactant when as progress emulsion polymerization, relative to whole 100 mass parts of amount of monomer, preferably For more than 0.3 mass parts and 3 below the mass.The usage amount of surfactant within the above range when, the water serial emulsion of acquisition Partial size become desired partial size, stable emulsion polymerization can be carried out, and can inhibit between positive active material and collector Closing force reduces.
Known usual free radical polymerization can be used to cause for the radical polymerization initiator used when as emulsion polymerization Agent can be enumerated such as ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide, tert-butyl hydroperoxide.In addition, as needed, it can also be with By the reducing agents such as these polymerization initiators and sodium hydrogensulfite, rongalite, ascorbic acid and with and carry out redox polymerization.
As the emulsion polymerization for obtaining resin binder of the invention, can be used the polymerization being added together, The method etc. being polymerize while continuously supplying each ingredient.Polymerization is usually in 30 DEG C or more, 90 DEG C of temperature ranges below Inside carry out under stiring.In addition, adjusting copolymerization by adding alkaline matter in polymerization or after polymerization in the present invention The pH of ethylenically unsaturated carboxylic acids, polymerization stability, mechanical stability, chemical stability when can be improved emulsion polymerization.As this When used alkaline matter, ammonia, triethylamine, ethanol amine, sodium hydroxide etc. can be used, a kind of or group can be used in they Close a variety of uses.
<(D) viscosifies dispersing agent>
In lithium ion secondary battery positive electrode slurry used in the present invention, in order to improve slurry positive active material that Around here and the cementability of positive electrode active material confrontation collector and improve slurry in positive active material dispersibility, improve slurry The stability of material, and with thickening dispersing agent.
As long as viscosifying dispersing agent water soluble polymer, there is no particular limitation, it is unrelated with having unprotected side chain or cross-linked structure, It can arbitrarily utilize.The water solubility of dispersibility as the positive active material that can be improved in lithium ion secondary battery positive electrode slurry It is derivative can to enumerate such as polyoxyalkylene, polyvinyl alcohol, poly carboxylic acid derivative's (including their salt), polycarboxylate for macromolecule Object, polyvinylamide etc..Particularly preferably containing selected from least one of polyoxyalkylene, polycarboxylic acids and polyvinylamide. Wherein, more preferably polyethylene oxide, polyacrylic acid and poly N-ethylene yl acetamide, acrylic acid and N- vinyl acetamide is total to The mixture of polymers, polyacrylic acid and poly N-ethylene yl acetamide.
In turn, as water soluble polymer, polysaccharide is also suitably, for the kind of sugared skeleton, bonding pattern, substituent group Class etc. does not limit, and can arbitrarily utilize.Especially from improving positive active material to each other and positive electrode active material confrontation collector Cementability viewpoint for, preferably carboxymethyl cellulose, carboxyethyl cellulose, carboxymethylethylcellulose, Methyl cellulose The cellulose derivatives such as element, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose (including they Salt).In addition, the carboxymethyl wherein more preferably using the viscosity that can assign appropriateness to lithium ion secondary battery positive electrode slurry is fine Dimension element.Here, as long as suitably as expected weight-average molecular weight, the degree of etherification falling of viscosity selection carboxymethyl cellulose are It can.
These water soluble polymers are it is preferable to use a kind of or a variety of uses of combination, using by the list of each water soluble polymer The copolymer of body copolymerization is also suitable.
Molecular weight for viscosifying the water soluble polymer of dispersing agent is not particularly limited, preferably according to manufacture lithium ion two The viscosity of the aqueous solution of the thickening dispersing agent used when primary cell anode slurry sets molecular weight.In addition, from positive slurry From the perspective of the thickening dispersion of material, the aqueous solution that 1 mass % viscosifies dispersing agent uses rotary viscosimeter (TVB- at 23 DEG C 25L, Dong Ji industry society manufacture) viscosity (mPa.s) under 60 turns be preferably 1~10000mPa.s, more preferably 10~ 2000mPa.s.Dispersed by using the thickening of the viscosity with above range, the solution viscosity for viscosifying dispersing agent is maintained at Desired viscosity, the dispersibility and positive active material of (A)~(C) ingredient in lithium ion secondary battery positive electrode slurry that Around here and the cementability of positive electrode active material confrontation collector improves, and slurry is excellent to the coating of collector.
In addition, 100 mass parts of solid component relative to positive active material, contain 0.2 mass parts or more and 5.0 mass Part thickening dispersing agent below, preferably contains 0.2 mass parts or more and 3.0 mass range below.By dispersing thickening The content of agent within the above range, can make positive active material evenly dispersed, can obtain the slurry for being suitble to the coating to collector Expect viscosity.
<(E) pH regulator>
It is used for for pH regulator of the invention by the pH tune of the aquo-lithium ion anode of secondary battery slurry at 23 DEG C The whole range for being 6.0~8.0.By the way that the pH of the positive slurry at 23 DEG C is adjusted to 6.0~8.0, it is able to suppress in anode With reacting for positive active material and the water in slurry.Moreover, the pH of more preferably positive slurry is 6.5~7.5 at 23 DEG C.
For positive slurry, it is however generally that the reactivity of water and lithium compound is very high, is noted to use and contain The positive active material of the transition metal oxide of lithium is easy to react with water in the stage for manufacturing positive slurry.As its reaction Mechanism, the lithium that can be enumerated in positive active material are disengaged in water in the form of lithium ion, react with water and generate lithium hydroxide.By It is influenced, and the pH of slurry generates various side reactions as the alkaline state for being more than 8.0.It is conceived in lithium ion secondary battery Side reaction, it is believed that the corrosion of the aluminium collector under basic conditions to anode can be promoted, the cementability of collector and active material is big Width reduces, to incur the low service life of battery.Additionally, it is believed that lithium hydroxide is reacted with carbonate-based solvent, lithium carbonate is obtained Or carbon dioxide etc., as secondary product, they can induce gas and produce or form electrode envelope, lead to the increase of cell resistance Or cell expansion.Moreover, the lithium in positive active material can be consumed because of these side reactions, therefore, it can be used for charge and discharge Lithium ion number is reduced, and battery capacity is caused to reduce.
Therefore, the pH of slurry is controlled in neutral region, is important in terms of maintaining lithium ion secondary battery characteristic.It is special It is not to eliminate strong basicity state in terms of the characteristic of positive slurry and be important, preferably by adding aftermentioned specific acid Inhibit the generation of hydroxide ion, inhibits the lithium to be detached from from positive active material.
Here, the useful method of the pH as control slurry, one is the battery electrode water system high using acid degree Adhesive or thickening dispersing agent, such as can enumerate using the high adhesive of the match ratio of ethylenically unsaturated carboxylic acids, polycarboxylic-acid increasing Viscous dispersing agent, but in order to realize that precision higher adjusts pH, make in slurry containing acid pH adjustment additive, these methods In wider range and subtle pH control can be carried out.
Above-mentioned pH regulator is selected from the compound containing organic acid, inorganic acid, and above-mentioned organic acid is selected from following compound, institute Compound is stated independent or compoundly containing at least one of 1 or more carboxyl, sulfo group and phosphonic acid base group, above-mentioned inorganic acid It is at least one kind of in phosphoric acid, boric acid, carbonic acid.
As above-mentioned organic acid, such as acetic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, heptan two can be enumerated It is acid, suberic acid, azelaic acid, decanedioic acid, phthalic acid, fumaric acid, citric acid, 1,2,3,4- butane tetracarboxylic acid, methanesulfonic acid, right Toluenesulfonic acid, camphorsulfonic acid, propyl phosphonous acid, vinyl phosphonic acid, phenyl-phosphonic acid, methylenediphosphonate etc..
In inorganic acid, preferably carbonic acid.In organic acid, preferably 1,2,3,4- butane tetracarboxylic acid, citric acid, succinic acid, Acetic acid, methanesulfonic acid, propyl phosphonous acid.
In addition, the pH regulator in the present invention is preferably weak acid from the viewpoint of the easiness that pH is adjusted.
Solid component for pH regulator used in anode slurry of the invention, relative to positive active material 100 mass parts add 0.1 mass parts or more and 1.0 below the mass, preferably add 0.2 mass parts or more and 0.8 mass parts Hereinafter, more preferably adding 0.3 mass parts or more and 0.7 below the mass.By the way that the content of pH regulator is set as above-mentioned model In enclosing, the remaining of the acid in anode can inhibit, the burn into that can inhibit aluminium collector as a result, inhibits collector and positive electrode active material Cementability between matter reduces.
On the other hand, it in the case where the pH of positive slurry is lower than 6.0 acidity, can also corrode aluminium collector, reduce Cementability between collector and active material becomes the factor for hindering battery long lifetime.In this case, it is preferred that by anode With the pH adjustment additive containing alkalinity in slurry, slurry is maintained at neutral range.
The type of pH adjustment additive as alkalinity, as long as the compound comprising organic base, inorganic base, does not just have It is particularly limited to, one of they can be used or is applied in combination a variety of.As organic base, can enumerate primary amine, secondary amine, tertiary amine, Quaternary ammonium salt can enumerate ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide etc., preferably alkalescent as inorganic base Ammonia.
<(F) water>
The water that decentralized medium as positive slurry of the invention uses is preferably to cross through ion exchange resin treatment Water (ion exchange water) and by processed water of reverse osmosis membrane water purification system (ultrapure water) etc..
[manufacturing method of lithium ion secondary battery positive electrode slurry]
For lithium ion secondary battery positive electrode slurry of the invention, be by (A) positive active material, (B) conductive auxiliary agent, (C) copolymerization comprising at least one of ethylenically unsaturated carboxylic acids ester and ethylenically unsaturated carboxylic acids with aromatic ethenyl compound Mixture made of the resin binder of object, (D) thickening dispersing agent, (E) pH regulator and (F) water dispersion or dissolution.Here, excellent It is selected as the slurry of aqueous dispersion, but in the range of not impacting to carrying capacity of environment, can also added and water hydrophily High solvent.
For the preparation of lithium ion secondary battery positive electrode slurry, for example following method can be enumerated: including alkene by (C) Belong to the resin of at least one of esters of unsaturated carboxylic acids and ethylenically unsaturated carboxylic acids and the copolymer of aromatic ethenyl compound Adhesive, (D) thickening dispersing agent, (E) pH regulator are dispersed or dissolved in (F) water (or solvent high with the compatibility of water), Then (A) positive active material, (B) conductive auxiliary agent are added.
[lithium ion secondary battery anode and its manufacturing method]
Lithium ion secondary battery anode of the invention contains: (A) positive active material, (B) conductive auxiliary agent, (C) include The tree of at least one of ethylenically unsaturated carboxylic acids ester and ethylenically unsaturated carboxylic acids and the copolymer of aromatic ethenyl compound Rouge adhesive, (D) viscosify dispersing agent, (E) pH regulator.
Here, about above-mentioned (A)~(E), it is same as described above, so omit the description herein.
The manufacturing method of lithium ion secondary battery anode of the invention is that have to live containing anode on positive electrode collector Property substance positive electrode active material layer anode manufacturing method, the manufacturing method have by above-mentioned lithium ion secondary battery just Pole is supplied with slurry to the process on above-mentioned positive electrode collector to form above-mentioned positive electrode active material layer.
Lithium ion secondary battery positive electrode for example and being coated on collector with slurry and be dry by anode of the invention Manufacture.General method can be used in the coating method of slurry of the invention, can enumerate such as reverse rollers method, direct roller method, scraper plate Method, scraper method, extrusion molding, spray process, intagliotype, stick coating method, dip coating and extrusion.
The one or two sides in collector can be implemented to the coating of collector in lithium ion secondary battery positive electrode slurry.? In the case where being coated on collector two sides, can while gradually be coated with, can also be coated with simultaneously on two sides.In addition, can also Continuously or to be intermittently coated on the surface of collector.The thickness of coating layer, length or width can be fitted according to the size of battery Work as decision.
General method can be used in the drying means of slurry of the invention.Particularly preferably be used alone or in combination hot wind, Vacuum, infrared ray, far infrared, electron beam and low temperature wind.Drying temperature is preferably 50 DEG C or more and 350 DEG C hereinafter, more preferably It is 50 DEG C or more and 200 DEG C or less.
As the collector of electrode for manufacturing the present invention, based on aluminium, without spy as long as metal material It does not limit.In addition, the shape of collector is also not particularly limited, but it is preferably generally and uses thickness 0.001mm or more and 0.5mm Flaky material below.Electrode of the invention can be suppressed as needed.General method can be used in drawing method, especially excellent Modeling has pressing or roll compacting method.Pressing pressure is not particularly limited, but preferably 0.1t/cm2Above and 10t/cm2Below.
[lithium ion secondary battery and its manufacturing method]
<lithium ion secondary battery>
Lithium ion secondary battery of the invention has anode of the invention.
As lithium ion secondary battery, it can enumerate and for example configure centre across permeability for cathode and anode of the invention Diaphragm (such as porous membrane of polyethylene or polypropylene), and wherein be impregnated with non-aqueous electrolyte obtained by non-water system two Primary cell；By by negative electrode layer is formed on collector two sides cathode/diaphragm/on the two sides of collector be formed with the sheet of anode layer The lamilate that the anode of invention/diaphragm is constituted is wound as cylinder shape (circinate), and resulting coiling body is held together with electrolyte It is contained in tubular non-aqueous secondary battery etc. obtained by metal shell with the end.
Metal exterior body or aluminium laminate case can be suitably used as the exterior body of shell in battery of the invention.Battery Shape be Coin shape, button type, piece type, cylinder type, rectangular, platypelloid type etc., be not particularly limited.
As the cathode for lithium ion secondary battery of the invention, such as it can be used and be formed on the current collector comprising negative Pole active material, adhesive negative electrode layer well known cathode.
As negative electrode active material, the usable negative electrode active material containing the element that can absorb and release lithium ion, Negative electrode active material well known to carbon material etc..
As negative electrode active material, as long as the material of lithium can be absorbed and be released, there is no particular limitation, non-stone can be used Inkization carbon, artificial graphite carbon, natural graphite carbon, lithium metal, the alloy of aluminium, lead, silicon, tin etc. and lithium, tin oxide, titanium oxide etc..
As the specific example of the above-mentioned negative electrode active material containing the element that can absorb and release lithium ion, example can be enumerated Such as metallic compound, metal oxide, lithium metal compounds, lithium metal oxide (including lithium-compound transition metal oxide) Deng.As the negative electrode active material of metallic compound form, LiAl, Li can be enumerated4Si、Li4.4Pb、Li4.4Sn etc..In addition, making For the negative electrode active material of metal oxide form, SnO, SnO can be enumerated2、GeO、GeO2、In2O、In2O3、PbO、PbO2、 Pb2O3、Pb3O4, SiO, ZnO etc..
As carbon material, such as graphite, amorphous carbon, carbon fiber, coke, activated carbon, carbon nanotube, carbon nanometer can be enumerated Carbon materials such as fiber, fullerene etc..
These negative electrode active materials can be used alone a kind, can also merge and use two or more.
In addition, the adhesive that can be used for cathode is not particularly limited, well known cathode adhesive resin can be used.
The material of collector as cathode, as long as conductive substance, can be used metal.As gold Belong to, is preferably not easy to form the metal of alloy with lithium, can specifically enumerate copper, nickel, iron, titanium, vanadium, chromium, manganese or their conjunction Gold.
As the shape of collector, film-form, netted, fibrous can be enumerated.Wherein, preferably film-form.Collector Thickness is preferably 5~30 μm, more preferably 8~25 μm.
As electrolyte, such as in the case where lithium ion secondary battery, can be used by as the lithium salts of electrolyte with 1M The concentration of left and right is dissolved in the electrolyte in non-water system organic solvent.
As lithium salts, such as LiClO can be enumerated4、LiBF4、LiI、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、 LiSbF6、LiAlCl4、LiCl、LiBr、LiB(C2H5)4、LiCH3SO3、LiC4F9SO3、Li(CF3SO2)2N、Li[(CO2)2]2B Deng.
On the other hand, as non-water system organic solvent, propylene carbonate, ethylene carbonate, butylene carbonate, carbon can be enumerated The carbonates such as dimethyl phthalate, diethyl carbonate, methyl ethyl carbonate；The lactones such as gamma-butyrolacton；Trimethoxy-methane, 1,2- The ethers such as dimethoxy-ethane, ether, 2- Ethoxyethane, tetrahydrofuran, 2- methyltetrahydrofuran；The sulfoxides such as dimethyl sulfoxide Class；The butyl oxide links classes such as 1,3- dioxolanes, penta ring of 4- methyl-1,3-dioxy；The nitrogenous class such as acetonitrile, nitromethane, NMP；Formic acid The esters such as methyl esters, methyl acetate, butyl acetate, methyl propionate, ethyl propionate, phosphotriester；Diethylene glycol dimethyl ether, triethylene glycol two The glymes class such as methyl ether, tetraethylene glycol dimethyl ether；The ketones such as acetone, metacetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK)； The sulfones class such as sulfolane；3- methyl -2-Oxazolidone etc.(oxazolidinon-5-yl-methyl)-2-thiophene-carboxamides；1,3- propane sultone, 4- butyl sultone, naphthalene sulphur Sultones class such as acid lactone etc..
Electrolyte can be used alone a kind, also two or more kinds may be used.
Lithium ion secondary battery for example can be by configuring the intermediate diaphragm across permeability for positive electrode and negative electrode, and at it It is middle impregnation non-water system electrolyte and obtain.
In addition, can be obtained as follows in the case where tubular.
Firstly, by by negative electrode layer is formed on collector two sides cathode/diaphragm/on the two sides of collector be formed with anode The lamilate that the anode of layer/diaphragm is constituted is wound as cylinder shape (circinate) to form coiling body.The coiling body of acquisition is held It is contained in metal shell with the end (battery case), cathode is connect with negative terminal, anode is connect with positive terminal.Then, It is impregnated with electrolyte in metal shell, then sealing metal shell, the lithium ion secondary battery of tubular is consequently formed.
<manufacturing method of lithium ion secondary battery>
The manufacturing method of lithium ion secondary battery of the invention is with the following process: preparing above-mentioned lithium ion secondary battery just The process of pole slurry；Above-mentioned lithium ion secondary battery positive electrode is coated on positive electrode collector with slurry and forms positive electrode active material Process of the matter layer to manufacture lithium ion secondary battery anode；Assembling have the lithium of above-mentioned lithium ion secondary battery anode from The process of sub- secondary cell.As the process of assembling lithium ion secondary battery, as long as by the lithium ion secondary electricity of present embodiment Pond uses anode to use as anode, is just not particularly limited.
[embodiment]
Hereinafter, the present invention is described in more detail based on embodiment, but the present invention is not limited to the following examples.This Outside, " part " and " % " in embodiment is to respectively refer to mass parts, quality % when without specializing.Obtained lithium in embodiment Ion secondary battery electrode slurry, the electrode for lithium ion secondary battery obtained using these slurries and use these electrodes Obtained lithium ion secondary battery and their benchmark test carries out by the following method.
[production of resin binder (Resin A)]
With condenser pipe, thermometer, blender, dropping funel detachable flask in be added ion exchange water 100 (Sanyo Chemical Industries, Ltd.'s manufacture, has trade name Eleminol JS-20 for mass parts and reactive anionic emulsifier Imitate ingredient 40%) 0.9 mass parts, it is warming up to 75 DEG C.Then, 4 hours are lasted and drip monomer emulsion, the monomer emulsion is In advance by 6.5 mass parts of above-mentioned reactive anionic emulsifier, (the first industrial pharmaceutical strain of non-reactive anion emulsifier The manufacture of formula commercial firm, trade name Hitenol 08E, polyethylene oxide alkyl ethers sulfuric acid) 1.2 mass parts, 149 mass of styrene Part, 131 mass parts of 2-EHA, 5.8 mass parts of 2-Hydroxyethyl methacrylate, acrylic acid (effective component 80%) 5.8 mass parts, 1.2 mass parts of sodium p styrene sulfonate, 1.5 parts of trimethylolpropane methacrylate and ion exchange water What 271 mass parts mixed.Meanwhile lasting 1.3 matter of potassium peroxydisulfate dripped as polymerization initiator at 80 DEG C for 4 hours Amount part is dissolved in solution obtained by 29 mass parts of ion exchange water, to be polymerize.It is cold after maturation in 2 hours after dropping liquid But to room temperature, 6.0 mass parts of ammonium hydroxide and 36 mass parts of ion exchange water is added, the lotion (solid component of Resin A is obtained 40.0%, the viscosity under 10 turns using rotary viscosimeter (TVB-25L, Toki Sangyo Co., Ltd. manufacture) at 23 DEG C: 1900mPa.s、pH6.7)。
[production of positive slurry]
According to the record of following Examples and Comparative Examples, adds resin binder and viscosify aqueous solution, the pH tune of dispersing agent Whole dose and water as needed, with planetary-type mixer, (プ ラ イ ミ Network ス Co., Ltd. manufactured, Ha イ ビ ス ミ ッ Network ス 2P- 03 type) be kneaded after, LiCo as a positive electrode active material is added in them1/3Ni1/3Mn1/3O2(hereinafter also referred to " NMC "), And the carbon black as conductive auxiliary agent, with planetary-type mixer, (プ ラ イ ミ Network ス Co., Ltd. manufactured, Ha イ ビ ス ミ ッ Network ス 2P- 03 type) it is kneaded, it is fabricated to anode slurry.
[pH of slurry is measured]
Under conditions of 1 atmospheric pressure, 23 DEG C, use pH meter (DKK Toa Corp.'s manufacture, product name: HM-30G) Measurement.
[positive production]
Positive slurry is coated on the aluminium foil as 20 μm of thickness of collector, so as to carry out the thickness after compression process As 60 μm, and it is 5 minutes dry at 50 DEG C with heating plate, and then drying after five minutes, uses mold press at 110 DEG C With pressing pressure 2.5t/cm2It is suppressed, collector plate is installed, anode is thus fabricated to.
[production of negative electrode slurry]
Relative to negative electrode active material (SCMG-BR (Showa Denko K. K's manufacture)) 100 mass parts, mixing is used as and leads 2 mass parts of carbon black (acetylene black) of electric auxiliary agent contain copolymer in cinnamic acrylic ester (Port リ ゾ ー Le as adhesive (" Port リ ゾ ー Le " is clear to LB-200 (Showa Denko K. K's manufacture, solid component 40%, viscosity 2000mPa.s, pH7.0) With the registered trademark of electrician Co., Ltd.)) 4 mass parts of emulsion polymer, as thickening dispersing agent by carboxymethyl cellulose (CMC) (viscosity at 23 DEG C of the CMC aqueous solution of 1 mass %: 1100mPa.s) is dissolved in CMC aqueous solution (the CMC concentration of water It for 2 mass %), 50 mass parts, and then adds 5 mass parts of water and is kneaded, be fabricated to negative paste.
[production of cathode]
Positive slurry is coated on the copper foil as 10 μm of thickness of collector, so as to carry out the thickness after compression process As 60 μm, with heating plate dry 5 minutes at 50 DEG C, then at 110 DEG C it is dry after five minutes, using mold press with Pressing pressure 2.5t/cm2It is suppressed, collector plate is installed, cathode is thus fabricated to.
[preparation of electrolyte]
Ethylene carbonate and diethyl carbonate are being mixed with volume ratio 2/3, dissolving LiPF in obtained in the mixed solvent6 The concentration for making 1.0mol/L, is prepared into electrolyte.
[production of battery]
Keep anode and cathode such as above-mentioned production opposed across the diaphragm of polyethylene, puts it into the container of aluminium layer pressure In, in the glove box under argon environment, above-mentioned electrolyte 1.0ml is added dropwise in the container for being put into above-mentioned electrode, depressurizes on one side It is thermally compressed lamination vessel on one side, is fabricated to battery.In addition, the theoretical capacity of the battery is designed as 16.5mAh.
[cell evaluation: initial capacity]
It is evaluated using day iron エ レ ッ Network ス charge/discharge testing device.After implementing aging process, in 25 DEG C of conditions Under, the CC-CV charging for carrying out 2 circulations (is charged to 0.2C (with the electric current of full charge and discharge in 5 hours) and reaches upper limit voltage (4.2V) is then charged to constant voltage (4.2V) by CV time (1.5 hours)) and CC electric discharge (be discharged to and reached with 0.2C To lower voltage limit (2.75V)).Being averaged for capacity when 2 CC are discharged is defined as the initial capacity of the battery.
[cell evaluation: initial DC resistance]
Initial capacity measurement after, under the conditions of 25 DEG C, 60% capacity of initial capacity is charged to 0.2C, then with 0.2C carries out CC and discharges 1 minute, the discharge current and voltage after measurement 1 second.Also same CC is carried out with 0.5C, 1.0C, 2.0C Electric discharge, discharge current and voltage after measurement respective 1 second, is drawn with each measured value, the slope of near linear is defined as the electricity The initial DC resistance in pond.
[cell evaluation: charge/discharge cycle characteristics]
Under the conditions of 45 DEG C, the CC-CV charging for repeating 150 circulations (is charged to 2C (with the electric current of 30 points of full charge and discharge) Reach upper limit voltage (4.2V), then charged to constant voltage (4.2V) by CV time (1.5 hours)) and CC electric discharge (with 2C is discharged to as lower voltage limit (2.75V)) Lai Jinhang.The charge/discharge cycle characteristics of battery are by acquiring capacity maintenance rate, i.e., The discharge capacity for acquiring the 150th circulation is compared relative to the ratio of the discharge capacity of the 1st circulation.
[embodiment 1]
In the production of positive slurry, with planetary-type mixer, (プ ラ イ ミ Network ス Co., Ltd. manufactured, Ha イ ビ ス ミ ッ Network ス 2P-03 type) to Resin A 1.25g (100 mass of solid component relative to positive active material as resin binder Part, the solid component of copolymer is 2.5 mass parts) and as thickening dispersing agent by carboxymethyl cellulose (hereinafter also referred to " CMC ") (the CMC aqueous solution of 1 mass % is in 23 DEG C of viscosity: 1100mPa.s) being dissolved in the CMC aqueous solution of water, (CMC concentration is 2 mass %) 20g (relative to 100 mass parts of solid component of positive active material, the solid component of CMC is 2.0 mass parts), And as pH regulator 1,2,3,4- butane tetracarboxylic acid is dissolved in water 1,2,3,4- butane tetracarboxylic aqueous acid (1,2,3, The concentration of 4- butane tetracarboxylic acid is 10 mass %) 1g (relative to 100 mass of positive active material, 1,2,3,4- butane tetracarboxylic acid Solid component be 0.5 mass parts) be kneaded, the LiCo of 20g as a positive electrode active material is then added in them1/ 3Ni1/3Mn1/3O2, as carbon black (acetylene black) 1g (100 mass of solid component relative to positive active material of conductive auxiliary agent Part, 5 mass parts are calculated as with solid component), further with planetary-type mixer, (プ ラ イ ミ Network ス Co., Ltd. manufactured, Ha イ ビ ス ミ ッ Network ス 2P-03 type) it is kneaded, it is fabricated to anode sizing agent.
[embodiment 2]
It, will be as the Resin A 1.25g of resin binder, inciting somebody to action as thickening dispersing agent in the production of positive slurry Polyethylene oxide (PEO) (viscosity at 23 DEG C of the PEO aqueous solution of 1 mass %: 12mPa.s) is dissolved in the PEO aqueous solution of water (PEO concentration is 10 mass %) the 4g and 1,2,3,4- that 1,2,3,4- butane tetracarboxylic acid is dissolved in water as pH regulator Butane tetracarboxylic aqueous acid (concentration of 1,2,3,4- butane tetracarboxylic acid is 10 mass %) 1g is mixed, and water is further added 10g is kneaded with planetary-type mixer (プ ラ イ ミ Network ス Co., Ltd. manufacture, Ha イ ビ ス ミ ッ Network ス 2P-03 type), is then existed The LiCo of 20g as a positive electrode active material is added in them1/3Ni1/3Mn1/3O2, as the carbon black (acetylene black) of conductive auxiliary agent 1g is kneaded with planetary-type mixer (プ ラ イ ミ Network ス Co., Ltd. manufacture, Ha イ ビ ス ミ ッ Network ス 2P-03 type), is fabricated to just Pole slurry.
[embodiment 3]
It, will be as the Resin A 1.25g of resin binder, inciting somebody to action as thickening dispersing agent in the production of positive slurry Poly N-ethylene yl acetamide (hereinafter also referred to " PNVA ") (viscosity at 23 DEG C of the PNVA aqueous solution of 1 mass %: 30mPa.s) It is dissolved in PNVA aqueous solution (PNVA concentration the be 10 mass %) 4g of water and as pH regulator by 1,2,3,4- butane tetracarboxylic Acid dissolution in water 1,2,3,4- butane tetracarboxylic aqueous acid (concentration of 1,2,3,4- butane tetracarboxylic acid be 10 mass %) 1g into Row mixing, further adds water 10g, and with planetary-type mixer, (プ ラ イ ミ Network ス Co., Ltd. manufactured, Ha イ ビ ス ミ ッ Network ス 2P-03 type) it is kneaded, the LiCo of 20g as a positive electrode active material is then added in them1/3Ni1/3Mn1/3O2, as conduction Carbon black (acetylene black) 1g of auxiliary agent, with planetary-type mixer, (プ ラ イ ミ Network ス Co., Ltd. manufactured, Ha イ ビ ス ミ ッ Network ス 2P- 03 type) it is kneaded, it is fabricated to anode sizing agent.
[embodiment 4]
It, will be as the Resin A 1.25g of resin binder, inciting somebody to action as thickening dispersing agent in the production of positive slurry Copolymer (copolymerization ratio 70/30) (hereinafter also referred to " PNVA/PAa ") (1 mass % of poly N-ethylene yl acetamide and polyacrylic acid 23 DEG C of PNVA/PAa aqueous solution at viscosity: 450mPa.s) be dissolved in PNVA/PAa aqueous solution (the PNVA/PAa concentration of water For 10 mass %) 4g and as the 1,2,3,4- butane tetracarboxylic that 1,2,3,4- butane tetracarboxylic acid is dissolved in water of pH regulator Aqueous acid (concentration of 1,2,3,4- butane tetracarboxylic acid is 10 mass %) 1g is mixed, is further added water 10g, use planet Formula mixer (manufacture of プ ラ イ ミ Network ス Co., Ltd., Ha イ ビ ス ミ ッ Network ス 2P-03 type) is kneaded, and is then added in them The LiCo of 20g as a positive electrode active material1/3Ni1/3Mn1/3O2, as carbon black (acetylene black) 1g of conductive auxiliary agent, use is planetary Mixer (manufacture of プ ラ イ ミ Network ス Co., Ltd., Ha イ ビ ス ミ ッ Network ス 2P-03 type) is kneaded, and is fabricated to anode sizing agent.
[embodiment 5]
In the production of positive slurry, the aqueous solution as pH regulator mixes 1,2,3,4- butane tetracarboxylic aqueous acids In addition to this 2g makes anode slurry in a manner of similarly to Example 1.
[embodiment 6]
In the production of positive slurry, the aqueous solution as pH regulator mixes 1,2,3,4- butane tetracarboxylic aqueous acids In addition to this 0.2g makes anode slurry in a manner of similarly to Example 1.
[embodiment 7]
In the production of positive slurry, use citric acid as pH regulator, and mixes aqueous citric acid solution (citric acid In addition to this concentration makes anode slurry for 10 mass %) 1g in a manner of similarly to Example 1.
[embodiment 8]
In the production of positive slurry, use succinic acid as pH regulator, and mixes butanedioic acid aqueous solution (succinic acid In addition to this concentration makes anode slurry for 10 mass %) 1g in a manner of similarly to Example 1.
[embodiment 9]
In the production of positive slurry, use acetic acid as pH regulator, and mixes acetic acid aqueous solution (acetic acid concentration is 10 mass %) in addition to this 1g makes anode slurry in a manner of similarly to Example 1.
[embodiment 10]
In the production of positive slurry, use methanesulfonic acid as pH regulator, and mixes aqueous methane sulfonic acid (methanesulfonic acid In addition to this concentration makes anode slurry for 10 mass %) 1g in a manner of similarly to Example 1.
[embodiment 11]
In the production of positive slurry, use propyl phosphonous acid as pH regulator, and mixes propyl phosphonous acid aqueous solution (third In addition to this base phosphonic acids concentration makes anode slurry for 10 mass %) 1g in a manner of similarly to Example 1.
[embodiment 12]
In the production of positive slurry, use carbonic acid as pH regulator, and mixed carbonic acid water aqueous solution (carbonate concentration Anode slurry is in addition to this made in a manner of similarly to Example 1 for 10 mass %) 1g.
[comparative example 1]
In the production of positive slurry, do not use resin binder, and add water 1.25g, in addition to this, with implementation The same mode of example 1 makes anode slurry.
[comparative example 2]
In the production of positive slurry, 1 as pH regulator is not mixed, 2,3,4- butane tetracarboxylic acid, in addition to this, Anode slurry is made in a manner of similarly to Example 1.
[comparative example 3]
In the production of positive slurry, 1 as pH regulator is not mixed, 2,3,4- butane tetracarboxylic acid, in addition to this, Anode slurry is made in a manner of similarly to Example 2.
[comparative example 4]
In the production of positive slurry, 1 as pH regulator is not mixed, 2,3,4- butane tetracarboxylic acid, in addition to this, Anode slurry is made in a manner of similarly to Example 3.
[comparative example 5]
In the production of positive slurry, 1 as pH regulator is not mixed, 2,3,4- butane tetracarboxylic acid, in addition to this, Anode slurry is made in a manner of similarly to Example 4.
[comparative example 6]
In the production of positive slurry, 1,2,3, the 4- butane tetracarboxylic aqueous acid 4g (phases as pH regulator are mixed It is 2.0 mass parts for 100 mass parts of solid component of positive active material), in addition to this, with side similarly to Example 1 Formula makes anode slurry.
[comparative example 7]
In the production of positive slurry, as resin binder, it is changed to containing SBR styrene butadiene rubbers ((SBR) 40 mass % of solid component) emulsion polymer anode slurry is in addition to this made in a manner of similarly to Example 1.
[comparative example 8]
In the production of positive slurry, as resin binder, it is changed to the emulsion polymer containing SBR, and do not mix Cooperation is in addition to this 1,2,3,4- butane tetracarboxylic acid of pH regulator make positive slurry in a manner of similarly to Example 1 Material.
[comparative example 9]
In the production of positive slurry, by 100 mass parts LiCo1/3Ni1/3Mn1/3O2, as the carbon black of conductive auxiliary agent (acetylene black) 5 mass parts, polyvinylidene fluoride (hereinafter also referred to " PVDF ") (KYNAR (the ARKEMA plants of formula meetings as adhesive Society's manufacture, the registered trademark that KYNAR be ARKEMA company) (concentration of PVDF for 10 mass %)) 10g mixed, further Addition N-Methyl pyrrolidone (NMP) 5g is simultaneously mixed, and is fabricated to anode slurry.
The pH of anode slurry, the result of various battery behaviors are shown in table 3.
[table 1]
Abbreviation in table is as follows.
NMC:LiCo1/3Ni1/3Mn1/3O2
CMC: carboxymethyl cellulose
PEO: polyethylene oxide
PNVA: poly N-ethylene yl acetamide
PNVA/PAa: the copolymer (copolymerization ratio 70/30) of poly N-ethylene yl acetamide and polyacrylic acid
[table 2]
Slightly note in table is as follows.
NMC:LiCo1/3Ni1/3Mn1/3O2
CMC: carboxymethyl cellulose
PEO: polyethylene oxide
PNVA: poly N-ethylene yl acetamide
PNVA/PAa: the copolymer (copolymerization ratio 70/30) of poly N-ethylene yl acetamide and polyacrylic acid
SBR: SBR styrene butadiene rubbers
PVDF: polyvinylidene fluoride
*1: the emulsion polymer containing SBR styrene butadiene rubbers (40 mass % of (SBR) solid component)
*2: polyvinylidene fluoride (PVDF) (KYNAR (manufacture of ARKEMA Co., Ltd., the note that KYNAR is ARKEMA company Volume trade mark) (concentration of PVDF is 10 mass %))
[table 3]
According to Examples 1 to 4 and comparative example 2~5 it is found that lithium ion secondary battery positive electrode slurry of the invention is not adding When adding pH regulator, pH is 9 or more deviation alkalinity, on the other hand, by adding additive, can be controlled its pH in differential gap Domain.Therewith, side reaction can be inhibited in lithium ion secondary battery, and can be inhibited in the positive active material with side reaction It can be used in the lithium consumption of charge and discharge, therefore, it can be stated that have both the high capacity characteristics, low resistance characteristic and high charge-discharge of battery Recycle sustainment rate characteristic.It is also shown that the fiber of water soluble polymer can be employed as with the thickening dispersing agent of adhesive Plain derivative, polyoxyalkylene, polycarboxylate, polycarboxylic acids and polyvinylamide, they can be with the shape of homopolymer or copolymer Formula uses.
According to embodiment 1,5~6 it is found that lithium ion secondary battery positive electrode of the invention passes through the suitable pH of addition with slurry Regulator shows excellent battery behavior.That is, showing to add 0.1~1.0 mass relative to 100 mass parts of positive active material When the pH regulator of part, excellent battery behavior is shown.When pH adjustment additive is excessively added such as comparative example 6, it is believed that because The pH of slurry is lower than 6.0, to generate the corrosion of aluminium collector, the cementability between active material and collector is greatly reduced, electricity Pond performance significantly deteriorates.
Show that the effect of the pH regulator of positive slurry not can be to whole according to embodiment 1 and comparative example 6~7 Resin binder is applicable in, and compared to SBR adhesive, contains ethylenically unsaturated carboxylic acids ester and ethylenically unsaturated carboxylic acids and aromatic series second The resin binder of the copolymer of alkenyl compound selectively shows the high charge-discharge circulation sustainment rate characteristic of battery.
Show that lithium ion secondary battery positive electrode slurry of the invention passes through addition according to Examples 1 to 4 and comparative example 9 PH adjustment use additive, have the effect of with the PVDF adhesive of previous dicyandiamide solution it is same or its more than.

Claims (10)

1. a kind of lithium ion secondary battery positive electrode slurry, which is characterized in that helped containing (A) positive active material, (B) conduction Agent, (C) resin binder, (D) thickening dispersing agent, (E) pH regulator and (F) water,
(C) resin binder includes following copolymers, and the copolymer is that ethylenically unsaturated carboxylic acids ester and olefinic are unsaturated The copolymer of at least one of carboxylic acid and aromatic ethenyl compound,
Relative to 100 mass parts of solid component of positive active material, the content of (E) the pH regulator be 0.1 mass parts with Upper and 1.0 below the mass, the pH of slurry is 6.1~7.7 at 23 DEG C.
2. lithium ion secondary battery positive electrode slurry according to claim 1, (E) the pH regulator is selected from comprising organic The compound of acid, inorganic acid,
The organic acid be selected from following compound, the compound independent or compoundly containing 1 or more carboxyl, sulfonic group and At least one of phosphonic acid base group,
The inorganic acid is selected from least one of phosphoric acid, boric acid and carbonic acid.
3. lithium ion secondary battery positive electrode slurry according to claim 1, (E) the pH regulator be selected from 1,2,3, At least one of 4- butane tetracarboxylic acid, citric acid, succinic acid, acetic acid, methanesulfonic acid, propane sulfonic acid, carbonic acid.
4. lithium ion secondary battery positive electrode slurry according to claim 1, (E) the pH regulator is that the pH of alkalinity is used Additive,
The pH of alkalinity additive is selected from the pH additive of organic basic, the pH additive of inorganic alkaline,
The pH additive of organic basic be selected from least one of primary amine, secondary amine, tertiary amine and quaternary ammonium,
The pH additive of inorganic alkaline be in ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide at least It is a kind of.
5. lithium ion secondary battery positive electrode slurry according to claim 1, relative to positive active material solid at Point 100 mass parts, containing it is more than 0.2 mass parts and 5.0 below the mass described in (C) resin binder.
6. lithium ion secondary battery positive electrode slurry according to claim 1, (D) thickening dispersing agent contain it is a kind of with On following water soluble polymers, the water soluble polymer includes carboxymethyl cellulose, polyethylene oxide, polyacrylic acid, poly- The copolymer of N- vinyl acetamide and acrylic acid and N- vinyl acetamide.
7. a kind of lithium ion secondary battery anode is using lithium ion secondary battery positive electrode slurry described in claim 1 Obtained from.
8. a kind of manufacturing method of lithium ion secondary battery anode, the lithium ion secondary battery anode is in positive electrode collector On have a positive electrode active material layer containing positive active material, the manufacturing method has to be supplied on the positive electrode collector The process that lithium ion secondary battery positive electrode described in claim 1 forms the positive electrode active material layer with slurry.
9. a kind of lithium ion secondary battery is using obtained from lithium ion secondary battery anode as claimed in claim 7.
10. a kind of manufacturing method of lithium ion secondary battery, with the following process: preparing lithium ion two described in claim 1 The process of primary cell anode slurry；The lithium ion secondary battery positive electrode is coated on positive electrode collector with slurry and is formed just Pole active material layer is come the process that manufactures lithium ion secondary battery anode；Assembling has the lithium ion secondary battery anode Lithium ion secondary battery process.
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