CN105940530A - Slurry for positive electrode of lithium ion secondary cell, positive electrode obtained using said slurry, method for manufacturing said positive electrode, lithium ion secondary cell formed using said positive electrode, and method for manufacturing said cell - Google Patents

Slurry for positive electrode of lithium ion secondary cell, positive electrode obtained using said slurry, method for manufacturing said positive electrode, lithium ion secondary cell formed using said positive electrode, and method for manufacturing said cell Download PDF

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CN105940530A
CN105940530A CN201580006248.1A CN201580006248A CN105940530A CN 105940530 A CN105940530 A CN 105940530A CN 201580006248 A CN201580006248 A CN 201580006248A CN 105940530 A CN105940530 A CN 105940530A
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positive electrode
acid
lithium ion
slurry
ion secondary
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CN105940530B (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

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

Abstract

A slurry for a positive electrode of a lithium ion secondary cell, said slurry containing (A) a positive electrode active material, (B) an electroconduction aid, (C) a resin binder comprising a copolymer of an aromatic vinyl compound and an ethylenically unsaturated carboxylate and/or an ethylenically unsaturated carboxylic acid, (D) a thickening dispersant, (E) a pH adjuster, and (F) water, the (E) pH adjuster content being 0.1-1.0 part by mass in relation to 100 parts by mass of the solids component of the positive electrode active material, and the pH of the slurry being 6.0-8.0 at 23 DEG C.

Description

Lithium ion secondary battery positive electrode slurry, use positive pole and manufacture method, use that this slurry obtains Lithium rechargeable battery and manufacture method thereof obtained by this positive pole
Technical field
The present invention relates to lithium ion secondary battery positive electrode slurry, the positive pole using this slurry to obtain and Manufacture method, use lithium rechargeable battery and manufacture method thereof obtained by this positive pole.
Background technology
Lithium rechargeable battery be widely used as the portable device such as mobile phone, laptop power supply, Electric power storage with or electric automobile etc. require the driving power supply of industry device of high life.From now on, The people's livelihood equipment requirements lightweight or miniaturization, it is desirable to there is the battery of higher energy density.It addition, In industry equipment, popularize along with electric automobile or the further of fixed pattern electric energy storage device, it is desirable to High output, Large Copacity, long-life performance corresponding to large-sized battery.
As realizing the high-energy-density of lithium rechargeable battery, high output, Large Copacity, long-life The means changed, improve the running voltage of positive pole, it is achieved the method for the high capacity of battery receives much concern. Such as, can stably store with the high voltage of more than 4.3V on the basis of lithium, release lithium and electronics With LiMO2The transition metal oxides containing lithium that (M is transition metal) represents etc. are as positive-active The exploitation of material is carried out.
It addition, the positive pole being used for lithium rechargeable battery is generally of and positive active material is stacked on aluminum The structure of collector body, in positive electrode active material layer, in addition to positive active material, is also used for Positive active material is bonded to each other and by bonding agent bonding with collector body for positive active material.In order to Realize the high power capacity of lithium rechargeable battery, long lifetime, as bonding agent, it is desirable to less amount and The material that bonding force is high.
During it is said that in general, lithium ion secondary battery positive electrode slurry is coated collector body to manufacture positive pole, As the binding agent of slurry, it is most widely used that and utilizes the N-Methyl pyrrolidone with organic solvent system (hereinafter also referred to " NMP ") is as the polyvinylidene fluoride (hereinafter also referred to " PVDF ") of solvent.
But, PVDF system binding agent can not by positive active material each other and active substance and collector body The most bonding, have the problem that the charge/discharge cycle characteristics of lithium rechargeable battery reduces.In reality During use, in order to ensure positive active material to each other and between active substance with collector body the most bonding Property, it is desirable to have substantial amounts of PVDF binding agent, result is that the capacity of lithium rechargeable battery can reduce. And, manufacturing because nmp solvent has a reason of mutagenicity etc. of PVDF system binding agent, thus ring Border load is high, is conceived to use water as the exploitation of the new binding agent of solvent.
On the other hand, in the exploitation of positive pole aqueous adhesive, it is widely used as negative pole water system The SBR styrene butadiene rubbers (hereinafter also referred to " SBR ") of binding agent receives much concern.It addition, pass through In aqueous solvent and be used as viscosify dispersant carboxymethyl cellulose (hereinafter also referred to " CMC "), Can carry out the manufacture that carrying capacity of environment is low, and realize positive active material to each other and active substance and current collection Good cementability between body.
But, it is low that the feature of its structure of SBR binding agent can enumerate non-oxidizability.Under high voltage condition Repeated charge, it is desirable in the positive pole of the lithium rechargeable battery of non-oxidizability, the profit of SBR binding agent Reduce by the long-life characteristics that may make battery.
And, it is however generally that the reactivity of water and lithium compound is the highest, make use of the transition containing lithium The stage that the positive active material of metal-oxide is noted manufacturing positive pole slurry is the most anti-with water Should, and imply that because of this reaction, thus lithium can depart from positive pole, can cause the fall of battery capacity Low or high resistance.Therefore, in the exploitation of positive pole aqueous adhesive, find in suppression slurry Positive active material is important with the method for the reaction of water.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 10-255808 publication
Patent documentation 2: Japanese Unexamined Patent Publication 10-241693 publication
Invent problem to be solved
It is an object of the invention to, it is provided that the lithium ion secondary battery positive electrode slurry of a kind of water system, make The positive pole obtained with this slurry and manufacture method thereof, use lithium rechargeable battery obtained by this positive pole and Its manufacture method, this slurry is the reaction that can suppress positive active material with water, it is possible to provide have both Gao Rong Flow characteristic, low resistance characteristic and the lithium rechargeable battery of high charge-discharge circulation sustainment rate characteristic.
For solving the means of problem
That is, system of the present invention is represented by following (1)～(10).
[1] a kind of lithium ion secondary battery positive electrode slurry, it is characterised in that containing (A) positive-active Material, (B) conductive auxiliary agent, (C) resin binder, (D) thickening dispersant, (E) pH regulator and (F) Water, described (C) resin binder comprises following copolymer, and described copolymer is ethylenically unsaturated carboxylic acids At least one in ester and ethylenically unsaturated carboxylic acids and the copolymer of aromatic ethenyl compound, relatively In solid constituent 100 mass parts of positive active material, the content of described (E) pH regulator is 0.1 More than mass parts and below 1.0 mass parts, the pH of slurry is 6.0～8.0 at 23 DEG C.
[2] according to the lithium ion secondary battery positive electrode slurry described in [1], wherein, described (E) pH adjusts Agent is selected from the compound comprising organic acid, mineral acid, and described organic acid is selected from following compound, described Compound individually or compoundly contains at least one base in carboxyl, sulfo group and the phosphonate group of more than 1 Group, described mineral acid at least one in phosphoric acid, boric acid and carbonic acid.
[3] according to the lithium ion secondary battery positive electrode slurry described in [1] or [2], wherein, described (E) pH Regulator is selected from 1,2,3,4-BTCA, citric acid, succinic acid, acetic acid, methanesulfonic acid, the third sulphur At least one in acid, carbonic acid.
[4] according to the lithium ion secondary battery positive electrode slurry described in [1] or [2], wherein, described (E) pH Regulator is the pH additive of alkalescence, and the pH of alkalescence additive is used selected from the pH of organic basic Additive, the pH additive of inorganic alkaline, the pH additive of organic basic be selected from primary amine, At least one in secondary amine, tertiary amine and quaternary ammonium, the pH additive of inorganic alkaline is selected from ammonia, hydrogen At least one in lithium oxide, sodium hydroxide, potassium hydroxide and calcium hydroxide.
[5] according to the lithium ion secondary battery positive electrode slurry according to any one of [1]～[4], wherein, phase For solid constituent 100 mass parts of positive active material, containing more than 0.2 mass parts and 5.0 mass Described (C) resin binder below part.
[6] according to the lithium ion secondary battery positive electrode slurry according to any one of [1]～[5], wherein, institute State the following water soluble polymer that (D) thickening dispersant contains more than one, described water soluble polymer bag Include carboxymethyl cellulose, poly(ethylene oxide), polyacrylic acid, poly-N-vinyl acetamide and acrylic acid Copolymer with N-vinyl acetamide.
[7] a kind of lithium ion secondary battery anode, is to use the lithium ion according to any one of [1]～[6] Anode of secondary battery slurry and obtain.
[8] manufacture method of a kind of lithium ion secondary battery anode, described lithium rechargeable battery is with just Pole possesses the positive electrode active material layer containing positive active material, described manufacturer on positive electrode collector Method just has on described positive electrode collector supply lithium rechargeable battery according to any one of [1]～[6] Pole slurry forms the operation of described positive electrode active material layer.
[9] a kind of lithium rechargeable battery, is to use the lithium ion secondary battery anode described in [7] to obtain Arrive.
[10] manufacture method of a kind of lithium rechargeable battery, has following operation: appoint in preparation [1]～[6] The operation of one described lithium ion secondary battery positive electrode slurry；By described lithium rechargeable battery just Pole slurry is coated positive electrode collector and is formed positive electrode active material layer to manufacture lithium rechargeable battery By the operation of positive pole；And assemble the lithium ion secondary electricity possessing described lithium ion secondary battery anode The operation in pond.
Invention effect
According to the present invention, and with specific resin binder with specifically viscosify dispersant, and then use The pH of aquo-lithium ion anode of secondary battery slurry is controlled the neutrality in 6.0～8.0 by pH regulator Region, by using this aquo-lithium ion anode of secondary battery slurry, it is possible to provide inhibit positive pole to use Positive active material in slurry and the reaction of water, have both high capacity characteristics, low resistance characteristic and height The lithium rechargeable battery of charge and discharge cycles sustainment rate characteristic and positive pole thereof.
Detailed description of the invention
Hereinafter, the present invention is described in detail.
[lithium ion secondary battery positive electrode slurry]
The lithium ion secondary battery positive electrode slurry of the present invention contains (A) positive active material, (B) conduction Auxiliary agent, (C) resin binder, (D) thickening dispersant, (E) pH regulator and (F) water, described (C) sets Fat binding agent comprises following copolymer, and described copolymer is ethylenically unsaturated carboxylic acids ester and olefinic unsaturation At least one in carboxylic acid and the copolymer of aromatic ethenyl compound, relative to positive active material Solid constituent 100 mass parts, the content of described (E) pH regulator is more than 0.1 mass parts and 1.0 Below mass parts, the pH of slurry is 6.0～8.0 at 23 DEG C.
<(A) positive active material>
As positive active material, as long as can be used for the positive active material of lithium rechargeable battery, Just it is not particularly limited, cobalt acid lithium (LiCoO can be used2), spinel lithium manganate (LiMn2O4), Fructus Canarii albi Stone-type LiFePO4 (LiFePO4), Ni-Mn-Co system, Ni-Mn-Al system and Ni-Co-Al system etc. contain Nickel lithium complex chemical compound, LiTiS2、LiMnO2、LiMoO3、LiV2O5Deng oxygen group compounds One in Deng or combine multiple use.
<(B) conductive auxiliary agent>
As conductive auxiliary agent, as long as having the material of electric conductivity, just it is not particularly limited, it is usually preferred to Use material with carbon element.As material with carbon element, as long as the material with carbon element with electric conductivity is just not particularly limited, Particularly preferably use the one in graphite, carbon black, carbon fiber etc. or combine multiple use.
As carbon black, such as acetylene black, Ketjen black, furnace black, channel black and thermal black can be enumerated, preferably For acetylene black, Ketjen black.
As for the content of conductive auxiliary agent, relative to solid constituent 100 mass parts of (A) composition, it is preferably More than 1 mass parts, below 10 mass parts, more than more preferably 2 mass parts, below 8 mass parts, More preferably more than 4 mass parts, below 6 mass parts.
<(C) resin binder>
Resin binder is at least one in ethylenically unsaturated carboxylic acids ester and ethylenically unsaturated carboxylic acids and virtue The copolymer of fragrant race vinyl compound.
Relative to solid constituent 100 mass parts of (A) positive active material, contain with solid component meter The resin binder of the present invention more than 0.2 mass parts and below 5.0 mass parts, preferably comprises 0.2 matter More than amount part below 3.0 mass parts.By being set to above-mentioned scope, it is provided that positive active material that Positive pole slurry that cementability around here and between positive active material and collector body is good and positive pole, and then By utilizing this positive pole, it is provided that there is high initial discharge capacity and excellent high temperature discharge and recharge follows The lithium rechargeable battery of ring property.Here, relative to the solid constituent 100 of (A) positive active material Mass parts, when resin binder is less than 0.2 mass parts, the cementability between active material and collector body The tendency reduced, during more than 5.0 mass parts, has the initial discharge capacity of lithium rechargeable battery to reduce Tendency.
At least one in ethylenically unsaturated carboxylic acids ester and ethylenically unsaturated carboxylic acids and aromatic vinyl Aromatic ethenyl compound in the copolymer of compound is to have olefinic carbon-to-carbon double bond and aromatic rings Compound.As aromatic ethenyl compound, can enumerate such as styrene, α-methyl styrene, Styrene sulfonic acid etc..As aromatic ethenyl compound, preferably styrene.
As ethylenically unsaturated carboxylic acids ester, such as α, β-unsaturated monocarboxylic acid or dicarboxylic acids (third can be enumerated Olefin(e) acid, methacrylic acid .beta.-methylacrylic acid, Yi Kang acid, maleic acid, fumaric acid etc.) Arrcostab, ester Alkyl chain is preferably carbon number 1～18, more preferably carbon number 2～12, more preferably carbon The straight-chain of atomic number 2～8, branched or ring-type alkyl chain.As ethylenically unsaturated carboxylic acids ester, Preferably there is (methyl) propylene of the straight-chain of carbon number 2～8, branched or ring-type alkyl chain Acid esters.Additionally, (methyl) acrylic acid is methacrylic acid or acrylic acid.
And, as long as not damaging positive active material to each other and between positive active material and collector body Cementability, then as in the ethylenically unsaturated carboxylic acids ester of resin binder and ethylenically unsaturated carboxylic acids Can also the following monomer of copolymerization in the copolymer of at least one and aromatic ethenyl compound: (methyl) Hydroxyalkyl acrylates, (methyl) acrylate, with vinyl acetate or alkyl acid second Alkene ester be the vinyl ester of representative, monoene hydro carbons (ethylene, propylene, butylene, isobutene. etc.), two Alkene (allene, methyl-prop diene, butadiene), diacetone acrylamide etc. are containing carbonyl olefinic insatiable hunger With monomer, containing sulfonic group ethylenically unsaturated monomer.These monomers can be a kind of or combine multiple.
In above-mentioned resin binder, live from the positive pole improved lithium ion secondary battery positive electrode slurry From the viewpoint of the dispersibility of property material, and in order to improve the characteristic of lithium rechargeable battery, and From the viewpoint of improving the non-oxidizability the resistance to stripping property to electrolyte and positive pole further, tree Fat binding agent is preferably styrene-(methyl) acrylate copolymer, styrene-(methyl) acrylic acid copolymer Thing or styrene-(methyl) acrylate-(methyl) acrylic copolymer, styrene-(methyl) acrylic acid Ester-acrylicstyrene sodium sulfonate copolymers, more preferably styrene-(methyl) Acrylate-Acrylic- Sodium styrene sulfonate copolymer.
Relative at least one in ethylenically unsaturated carboxylic acids ester and ethylenically unsaturated carboxylic acids and aromatic series second Copolymer structure unit 100 molar part of alkenyl compound, the content of ethylenically unsaturated carboxylic acids ester units It is preferably more than 25 molar part and below 85 molar part, more than more preferably 30 molar part and 80 rub Below your part.By making the content of ethylenically unsaturated carboxylic acids ester units within the above range, it is thus achieved that just The flexibility of pole, thermostability improve, and positive active material is to each other and between active substance and collector body Cementability improve.
Relative at least one in ethylenically unsaturated carboxylic acids ester and ethylenically unsaturated carboxylic acids and aromatic series second Copolymer structure unit 100 molar part of alkenyl compound, the content of ethylenically unsaturated carboxylic acids unit is excellent Elect below more than 1 molar part and 10 molar part as, more than more preferably 1 molar part and 5 molar part with Under.By making the content of ethylenically unsaturated carboxylic acids monomeric unit within the above range, aromatic series can be maintained The stability of emulsion polymerization of the copolymer of vinyl compound and ethylenically unsaturated carboxylic acids or mechanically stable Property, positive active material cementability to each other and between positive active material and collector body improves.
It addition, the resin binder of the present invention, particularly ethylenically unsaturated carboxylic acids ester and olefinic are unsaturated At least one in carboxylic acid and the copolymer of aromatic ethenyl compound, as required, it is also possible to will The α, β containing epoxy radicals such as (methyl) glycidyl acrylate as cross-linking agent-olefinic unsaturation chemical combination Thing, VTES, γ-acryloxypropyl trimethoxy silanes etc. are containing water-disintegrable alkane The α of epoxide silicyl, β-alefinically unsaturated compounds, ethylene glycol bisthioglycolate (methyl) acrylate, three hydroxyls Methylpropane three (methyl) acrylate, (methyl) allyl acrylate, divinylbenzene, adjacent benzene two The monomers such as the polyfunctional vinyl compounds such as formic acid diallyl import as being total to that positive electrode binder uses In polymers so that it is itself be cross-linked to each other or become with the alefinically unsaturated compounds of active hydrogen group It is grouped incompatible crosslinking.Alternatively, it is also possible to by the α containing carbonyl, β-alefinically unsaturated compounds etc. imports In copolymer, can with many hydrazine compounds, particularly grass acid dihydrazide, succinum acid dihydrazide, oneself two Acid dihydrazide, polypropylene acid dihydrazide etc. have the compound combination of more than 2 hydrazide groups and cross-link.
For obtain the present invention resin binder, especially for obtain ethylenically unsaturated carboxylic acids ester and The side of polymerization of at least one in ethylenically unsaturated carboxylic acids and the copolymer of aromatic ethenyl compound Method, can use currently known method, emulsion polymerization is preferably used.Use when being polymerized as emulsion Surfactant, common anionic surfactant, nonionic surfactant can be used. As anionic surfactant, such as alkylbenzenesulfonate, alkyl sulfate salt can be enumerated, gather Oxirane alkyl ether sulphate salts, soap etc., as nonionic surfactant, can lift Go out polyethylene oxide alkyl ethers, poly(ethylene oxide) alkyl phenyl ether, the multi-ring phenyl ether of poly(ethylene oxide), Polyoxyalkylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid Ester etc..These surfactants can use one or combine multiple use.
As for the usage amount of the surfactant carried out when emulsion is polymerized, relative to whole amount of monomer 100 Mass parts, more than preferably 0.3 mass parts and below 3 mass parts.The usage amount of surfactant exists Time in above-mentioned scope, it is thus achieved that the particle diameter of water serial emulsion become desired particle diameter, stable breast can be carried out Liquid is polymerized, and the closing force between positive active material and collector body can be suppressed to reduce.
The radical polymerization initiator used when being polymerized as emulsion, can use known usual free radical Polymerization initiator, can enumerate such as Ammonium persulfate., potassium peroxydisulfate, hydrogen peroxide, tert-butyl hydroperoxide Hydrogen etc..It addition, as required, it is also possible to by these polymerization initiators and sodium sulfite, rongalite, The reducing agents such as ascorbic acid and with and carry out redox polymerization.
As the emulsion polymerization of resin binder for obtaining the present invention, can use and add in the lump Polymerization, the most continuously each composition of supply are while carrying out the method etc. being polymerized.Polymerization is generally at 30 DEG C Above, under agitation carry out within the scope of the temperature of less than 90 DEG C.Additionally, by polymerization in the present invention In or polymerization terminate after add alkaline matter to adjust the pH of the ethylenically unsaturated carboxylic acids of copolymerization, can carry The polymerization stability during polymerization of high emulsion, mechanical stability, chemical stability.As now being used Alkaline matter, ammonia, triethylamine, ethanolamine, sodium hydroxide etc. can be used, they can use A kind of or combine multiple use.
<(D) viscosifies dispersant>
In the lithium ion secondary battery positive electrode slurry used in the present invention, in order to improve the positive pole of slurry Active substance is to each other and the cementability of positive electrode active material confrontation collector body and improve the positive pole in slurry The dispersibility of active substance, the stability of raising slurry, and with viscosifying dispersant.
As long as thickening dispersant water soluble polymer, just it is not particularly limited, and has unprotected side chain or friendship Connection structure is unrelated, can arbitrarily utilize.As just improving in lithium ion secondary battery positive electrode slurry The water soluble polymer of the dispersibility of pole active substance, can enumerate such as polyoxyalkylene, polyvinyl alcohol, Poly carboxylic acid derivative's (including their salt), polycarboxylate derivant, polyvinylamide etc..Special Do not preferably comprise at least one in polyoxyalkylene, polycarboxylic acids and polyvinylamide.Wherein, More preferably poly(ethylene oxide), polyacrylic acid and poly N-ethylene yl acetamide, acrylic acid and N-ethylene The copolymer of yl acetamide, polyacrylic acid and the mixture of poly N-ethylene yl acetamide.
And then, as water soluble polymer, polysaccharide is also suitable, for sugar skeleton, bonding side Formula, the kind etc. of substituent group do not limit, and can arbitrarily utilize.Particularly from improving positive active material To each other and positive electrode active material confrontation collector body cementability viewpoint for, preferably carboxymethyl cellulose Element, carboxyethyl cellulose, carboxymethylethylcellulose, methylcellulose, ethyl cellulose, hydroxyl first The cellulose derivatives such as base cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose (include their salt Class).Lithium ion secondary battery positive electrode slurry imparting appropriateness can be glued additionally, the most more preferably use The carboxymethyl cellulose of property.As long as here, suitably selecting carboxymethyl cellulose according to desired viscosity The weight-average molecular weight of element, degree of etherification falling.
These water soluble polymers are preferably used one or combine multiple use, use each water solublity The copolymer of high molecular monomer copolymerization is also suitable.
It is not particularly limited, preferably according to system for viscosifying the molecular weight of the water soluble polymer of dispersant The viscosity of the aqueous solution of the thickening dispersant used when making lithium ion secondary battery positive electrode slurry sets Molecular weight.It addition, from the viewpoint of the thickening of positive pole slurry disperses, 1 mass % thickening dispersion The aqueous solution of agent uses rotary viscosimeters (TVB-25L, Dong Ji industry society manufacture) 60 at 23 DEG C Viscosity (mPa.s) under Zhuaning is preferably 1～10000mPa.s, more preferably 10～2000mPa.s. Had the thickening dispersion of the viscosity of above-mentioned scope by use, the solution viscosity of thickening dispersant is protected Hold (A)～(C) composition in desired viscosity, lithium ion secondary battery positive electrode slurry dispersibility, And positive active material to each other and positive electrode active material confrontation collector body cementability improve, slurry is to collection The coating of electricity body is excellent.
It addition, relative to solid constituent 100 mass parts of positive active material, containing 0.2 mass parts Thickening dispersant above and below 5.0 mass parts, is preferably and contains more than 0.2 mass parts and 3.0 matter Measure following scope.By making the content of thickening dispersant within the above range, positive-active can be made Material is dispersed, can obtain being suitable for the slurry viscosity of the coating to collector body.
<(E) pH regulator>
PH regulator for the present invention is used for using the aquo-lithium ion anode of secondary battery at 23 DEG C The pH of slurry is adjusted to the scope of 6.0～8.0.By the pH of the positive pole slurry at 23 DEG C is adjusted It is 6.0～8.0, it is possible to suppress the reaction of the positive active material in positive pole slurry and water.And, The more preferably pH of positive pole slurry is 6.5～7.5 at 23 DEG C.
For positive pole slurry, it is however generally that water is the highest with the reactivity of lithium compound, is noted Have employed the positive active material of the transition metal oxide containing lithium in the stage manufacturing positive pole slurry Easily react with water.As its response mechanism, the lithium in positive active material can be enumerated with lithium ion shape Formula is disengaged in water, reacts with water and generates Lithium hydrate.Being affected by, the pH of slurry becomes super Cross the alkaline state of 8.0, produce various side reaction.The side reaction being conceived in lithium rechargeable battery, Thinking and can promote under basic conditions the corrosion of the aluminum collector body to positive pole, collector body is viscous with active substance Connecing property is greatly reduced, thus causes the low life-span of battery.Additionally, it is believed that Lithium hydrate and carbonic ester Series solvent reacts, and obtains the secondary product of the conduct such as lithium carbonate or carbon dioxide, and they can induce gas and produce Life or formation electrode tunicle, cause increase or the cell expansion of cell resistance.And, because these are secondary Reaction, the lithium in positive active material can be consumed, and therefore, the lithium ion number that can be used for discharge and recharge subtracts Few, cause battery capacity to reduce.
Therefore, the pH of slurry is controlled at neutral region, maintaining lithium rechargeable battery characteristic side Face is important.Particularly in terms of the characteristic of positive pole slurry, it is important for eliminating strong basicity state, Preferably suppress the generation of hydroxide ion by adding specific acid described later, suppression lithium is from positive pole Active substance departs from.
Here, as the useful method of the pH controlling slurry, the first uses the electricity that acidity degree is high Pond electrode water system binding agent or thickening dispersant, such as, can enumerate and use joining of ethylenically unsaturated carboxylic acids Binding agent, polycarboxylic-acid that composition and division in a proportion is high viscosify dispersant, but higher adjust pH to realize precision, Make in slurry containing acid pH adjustment additive, these methods can in widely scope and Carry out trickle pH to control.
Above-mentioned pH regulator is selected from containing organic acid, the compound of mineral acid, and above-mentioned organic acid is selected from Following compound, described compound individually or compoundly contains carboxyl, sulfo group and the phosphonic acids of more than 1 At least one group in base, above-mentioned mineral acid at least one in phosphoric acid, boric acid, carbonic acid.
As above-mentioned organic acid, can enumerate such as acetic acid, oxalic acid, malonic acid, succinic acid, 1,3-propanedicarboxylic acid, Adipic acid, 1,5-pentanedicarboxylic acid., suberic acid, Azelaic Acid, decanedioic acid, phthalic acid, fumaric acid, Fructus Citri Limoniae Acid, 1,2,3,4-BTCA, methanesulfonic acid, p-methyl benzenesulfonic acid, camphorsulfonic acid, propyl phosphonous acid, second Alkenyl phosphonic acid, phenyl-phosphonic acid, methylenediphosphonate etc..
In mineral acid, preferably carbonic acid.In organic acid, preferably 1,2,3,4-BTCAs, Fructus Citri Limoniae Acid, succinic acid, acetic acid, methanesulfonic acid, propyl phosphonous acid.
It addition, from the viewpoint of the easiness that pH adjusts, the pH regulator in the present invention is preferred For weak acid.
For the pH regulator used in the positive pole slurry of the present invention, relative to positive active material Solid constituent 100 mass parts, add below more than 0.1 mass parts and 1.0 mass parts, preferably add Add below more than 0.2 mass parts and 0.8 mass parts, more preferably add more than 0.3 mass parts and 0.7 Below mass parts.By the content of pH regulator is set in above-mentioned scope, can suppress in positive pole The remaining of acid, thus, can suppress between the burn into suppression collector body of aluminum collector body and positive active material Cementability reduce.
On the other hand, in the case of the pH of positive pole slurry is less than the acidity of 6.0, also can corrode Aluminum collector body, reduces the cementability between collector body and active substance, becomes and hinders battery long lifetime Factor.In the case of Gai, preferably by containing the pH adjustment additive of alkalescence in positive pole slurry, Slurry is maintained at neutral range.
As the kind of pH adjustment additive of alkalescence, as long as comprise organic base, inorganic base Compound, is just not particularly limited, it is possible to use one in them or be applied in combination multiple.Make For organic base, primary amine, secondary amine, tertiary amine, quaternary ammonium salt can be enumerated, as inorganic base, can enumerate ammonia, Lithium hydrate, sodium hydroxide, potassium hydroxide, calcium hydroxide etc., the most weakly alkaline ammonia.
<(F) water>
The water used as the disperse medium of the positive pole slurry of the present invention is preferably through ion exchange resin The water (ion exchange water) processed and the water (ultra-pure water) processed by reverse osmosis membrane water cleaning systems Deng.
[manufacture method of lithium ion secondary battery positive electrode slurry]
For the lithium ion secondary battery positive electrode slurry of the present invention, it is by (A) positive active material, (B) Conductive auxiliary agent, (C) comprise at least one in ethylenically unsaturated carboxylic acids ester and ethylenically unsaturated carboxylic acids and virtue The resin binder of copolymer of fragrant race vinyl compound, (D) viscosify dispersant, (E) pH regulator And (F) water-dispersible or dissolve mixture.Here, the slurry of preferably aqueous dispersion, but In the range of carrying capacity of environment not being impacted, it is also possible to add the solvent high with water hydrophilic.
For the preparation of lithium ion secondary battery positive electrode slurry, following method can be enumerated: (C) is comprised at least one in ethylenically unsaturated carboxylic acids ester and ethylenically unsaturated carboxylic acids and aromatic series second The resin binder of the copolymer of alkenyl compound, (D) thickening dispersant, (E) pH regulator dispersion or It is dissolved in (F) water (or solvent high with the affinity of water), then adds (A) positive active material, (B) Conductive auxiliary agent.
[lithium ion secondary battery anode and its manufacture method]
The lithium ion secondary battery anode of the present invention contains: (A) positive active material, (B) conduction help Agent, (C) comprise at least one in ethylenically unsaturated carboxylic acids ester and ethylenically unsaturated carboxylic acids and aromatic series second The resin binder of the copolymer of alkenyl compound, (D) viscosify dispersant, (E) pH regulator.
Here, about above-mentioned (A)～(E), same as described above, so omit the description herein.
The manufacture method of the lithium ion secondary battery anode of the present invention is to possess to contain on positive electrode collector The manufacture method of the positive pole of the positive electrode active material layer of positive active material, described manufacture method is had to have Above-mentioned lithium ion secondary battery positive electrode slurry is supplied to above-mentioned positive electrode collector thus is formed above-mentioned The operation of positive electrode active material layer.
The positive pole of the present invention is such as by coating lithium ion secondary battery positive electrode slurry on collector body And be dried and manufacture.The coating process of the slurry of the present invention can use general method, can enumerate such as Reverse rollers method, direct roller method, scraper plate method, doctor blade method, extrusion molding, spray process, intagliotype, rod are coated with Method, dip coating and squeezing and pressing method.
Lithium ion secondary battery positive electrode slurry can be implemented on the one side of collector body to the coating of collector body Or two sides.In the case of coating collector body two sides, can one side one side ground gradually coating, can also It is coated with on two sides simultaneously.Alternatively, it is also possible to continuously or be coated with intermittently on the surface of collector body.It is coated with The thickness of layer of cloth, length or width suitably can determine according to the size of battery.
The drying means of the slurry of the present invention can use general method.The most alone or in combination Use hot blast, vacuum, infrared ray, far infrared, electron beam and low warm air.Baking temperature is preferably More than 50 DEG C and less than 350 DEG C, more preferably more than 50 DEG C and less than 200 DEG C.
As the collector body of the electrode for manufacturing the present invention, based on aluminum, as long as metal material Material is just not particularly limited.It addition, the shape of collector body is also not particularly limited, but it is preferably generally Use more than thickness 0.001mm and the flaky material of below 0.5mm.The electrode of the present invention can basis Needs are suppressed.Drawing method can use general method, particularly preferred mould pressing or roll compacting Method.Pressing pressure is not particularly limited, but preferably 0.1t/cm2Above and 10t/cm2Below.
[lithium rechargeable battery and its manufacture method]
<lithium rechargeable battery>
The lithium rechargeable battery of the present invention possesses the positive pole of the present invention.
As lithium rechargeable battery, can enumerate and such as the positive pole of negative pole and the present invention is configured to centre Across the barrier film (porous membrane of such as polyethylene or polypropylene) of permeability, and it is impregnated with non-wherein Non-aqueous secondary battery obtained by aqueous electrolyte；By by being formed with the negative of negative electrode layer on collector body two sides The lamilated body that the positive pole of the present invention of pole/barrier film/be formed on the two sides of collector body anode layer/barrier film is constituted It is wound as cylinder shape (swirling), the coiling body of gained is contained in metal with the end together with electrolyte Tubular non-aqueous secondary battery etc. obtained by housing.
The battery of the present invention, as the exterior body of housing, can suitably use metal exterior body or aluminium lamination pressure Exterior body.Battery be shaped as Coin shape, button type, flap-type, cylinder type, square, platypelloid type etc., It is not particularly limited.
As the negative pole of the lithium rechargeable battery for the present invention, such as, it is usable in shape on collector body Become to have the known negative pole of the negative electrode layer comprising negative electrode active material, binding agent.
As negative electrode active material, can use containing can occlusion and release the negative pole of element of lithium ion The known negative electrode active material such as active substance, material with carbon element.
As negative electrode active material, as long as can occlusion and release the material of lithium, be just not particularly limited, Ungraphitised carbon, Delanium carbon, native graphite carbon, lithium metal, aluminum, lead, silicon, stannum can be used Deng the alloy with lithium, stannum oxide, titanium oxide etc..
As above-mentioned containing can occlusion and release the concrete example of negative electrode active material of element of lithium ion Son, can enumerate such as metallic compound, metal-oxide, lithium metal compounds, lithium metal oxide (bag Include lithium-compound transition metal oxide) etc..As the negative electrode active material of metallic compound form, can Enumerate LiAl, Li4Si、Li4.4Pb、Li4.4Sn etc..It addition, as the negative pole of metal-oxide form Active substance, can enumerate SnO, SnO2、GeO、GeO2、In2O、In2O3、PbO、PbO2、 Pb2O3、Pb3O4, SiO, ZnO etc..
As material with carbon element, can enumerate such as graphite, amorphous carbon, carbon fiber, coke, activated carbon, The material with carbon elements etc. such as CNT, carbon nano-fiber, fullerene.
These negative electrode active materials can be used alone a kind, it is also possible to merges and uses two or more.
It addition, the binding agent that can be used for negative pole is not particularly limited, known negative pole can be used to bond Agent resin.
As the material of the collector body of negative pole, as long as have the material of electric conductivity, gold can be used Belong to.As metal, be preferably difficult to and lithium form the metal of alloy, specifically can enumerate copper, nickel, Ferrum, titanium, vanadium, chromium, manganese or their alloy.
As the shape of collector body, film like, netted, fibrous can be enumerated.Wherein, the thinnest Membranaceous.The thickness of collector body is preferably 5～30 μm, more preferably 8～25 μm.
As electrolyte, such as in the case of lithium rechargeable battery, can use will be as electrolyte Lithium salts be dissolved in the electrolyte in non-water system organic solvent with the concentration of about 1M.
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 etc..
On the other hand, as non-water system organic solvent, can enumerate propylene carbonate, ethylene carbonate, The carbonates such as butylene carbonate, dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate；γ-Ding Nei The lactone such as ester；Trimethoxy-methane, 1,2-dimethoxy-ethane, ether, 2-Ethoxyethane, four The ethers such as hydrogen furan, 2-methyltetrahydrofuran；The sulfoxide types such as dimethyl sulfoxide；1,3-dioxolanes, 4- The butyl oxide link classes such as methyl-1,3-dioxy penta ring；The nitrogenous classes such as acetonitrile, nitromethane, NMP；Formic acid first The esters such as ester, methyl acetate, butyl acetate, methyl propionate, ethyl propionate, phosphotriester；Two is sweet The glyme classes such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether., tetraethylene glycol dimethyl ether；Acetone, diethyl The ketones such as ketone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK)；The sulfone classes such as sulfolane；3-methyl-2-Oxazolidine Ketone etc.(oxazolidinon-5-yl-methyl)-2-thiophene-carboxamides；In the sulfonic acid such as 1,3-propane sultone, 4-butyl sultone, LOMAR PWA EINECS 246-676-2 lactone Esters etc..
Electrolyte can be used alone a kind, and can also be used two or more.
Lithium rechargeable battery such as can by positive pole and negative pole are configured to middle across permeability every Film, and be impregnated with the electrolyte of non-water system wherein and obtain.
It addition, in the case of tubular, can obtain as follows.
First, by by being formed with the negative pole/barrier film of negative electrode layer/on the two sides of collector body on collector body two sides The lamilated body of the positive pole/barrier film composition being formed with anode layer is wound as cylinder shape (swirling) thus forms volume Around body.The coiling body of acquisition is contained in metal shell with the end (battery case), by negative pole and negative pole Terminal connects, and is connected with positive terminal by positive pole.Then, metal shell is impregnated with electrolyte, so Rear sealing metal housing, is consequently formed the lithium rechargeable battery of tubular.
<manufacture method of lithium rechargeable battery>
The manufacture method of the lithium rechargeable battery of the present invention has following operation: prepare above-mentioned lithium ion The operation of anode of secondary battery slurry；Above-mentioned lithium ion secondary battery positive electrode slurry is just coated Electrode current collector also forms positive electrode active material layer thus manufactures the operation of lithium ion secondary battery anode； Assemble the operation of the lithium rechargeable battery possessing above-mentioned lithium ion secondary battery anode.As assembling The operation of lithium rechargeable battery, if using the lithium ion secondary battery anode of present embodiment as Positive pole uses, and is just not particularly limited.
[embodiment]
Hereinafter, the present invention is described in more detail based on embodiment, but the present invention is not appointed by following example What limits.Additionally, " part " and " % " in embodiment is to refer to quality respectively when without specializing Part, quality %.In embodiment obtained by electrode slurry for lithium ion secondary battery, use these to starch Expect the electrode for lithium ion secondary battery obtained and the lithium rechargeable battery using these electrodes to obtain And their benchmark test is carried out by the following method.
[making of resin binder (Resin A)]
The detachable flask with condensing tube, thermometer, blender, Dropping funnel adds from Sub-exchanged water 100 mass parts and reactive anionic emulsifier (Sanyo Chemical Industries, Ltd.'s system Make, trade name Eleminol JS-20, effective ingredient 40%) 0.9 mass parts, be warming up to 75 DEG C.Connect , last 4 hours and drip monomer emulsion, described monomer emulsion is in advance by above-mentioned reactive cloudy Ionic emulsifier 6.5 mass parts, (the first industrial pharmaceutical strain formula meeting of non-reactive anion emulsifying agent Society's manufacture, trade name Hitenol 08E, polyethylene oxide alkyl ethers sulfuric acid) 1.2 mass parts, benzene Ethylene 149 mass parts, 2-EHA 131 mass parts, HEMA 5.8 Mass parts, acrylic acid (effective ingredient 80%) 5.8 mass parts, sodium p styrene sulfonate 1.2 mass parts, Trimethylolpropane methacrylate 1.5 parts and ion exchange water 271 mass parts mix. Meanwhile, potassium peroxydisulfate 1.3 mass parts dripped as polymerization initiator at 80 DEG C for 4 hours is lasted It is dissolved in solution obtained by ion exchange water 29 mass parts, thus is polymerized.After dropping liquid terminates, 2 It is cooled to room temperature after hour maturation, adds ammonia 6.0 mass parts and ion exchange water 36 mass parts, To Resin A emulsion (use rotary viscosimeter at solid constituent 40.0%, 23 DEG C (TVB-25L, Toki Sangyo Co., Ltd. manufacture) 10 turns under viscosity: 1900mPa.s, pH6.7).
[making of positive pole slurry]
According to following embodiment and the record of comparative example, add resin binder and the water of thickening dispersant Solution, pH regulator and water as required, by planetary-type mixer (プ ラ イ ミ Network ス strain formula Commercial firm manufactures, Ha イ PVC ス ミ ッ Network ス 2P-03 type) after kneading, add in them and live as positive pole The LiCo of property material1/3Ni1/3Mn1/3O2(hereinafter also referred to " NMC ") and the carbon as conductive auxiliary agent Black, with planetary-type mixer, (プ ラ イ ミ Network ス Co., Ltd. manufactures, Ha イ PVC ス ミ ッ Network ス 2P-03 Type) kneading, it is fabricated to positive pole slurry.
[pH of slurry measures]
At 1 atmospheric pressure, under conditions of 23 DEG C, use pH meter (DKK Toa Corp. manufactures, Goods name: HM-30G) measure.
[making of positive pole]
Aluminium foil as thickness 20 μm of collector body is coated with positive pole slurry, so that suppressing Thickness after process becomes 60 μm, and is dried 5 minutes at 50 DEG C by heating plate, then at 110 DEG C Under be dried 5 minutes after, use mould press with pressing pressure 2.5t/cm2Suppress, collection is installed Electricity sheet, is thus fabricated to positive pole.
[making of cathode size]
Relative to negative electrode active material (SCMG-BR (Showa Denko K. K's manufacture)) 100 mass parts, Mix as carbon black (acetylene black) 2 mass parts of conductive auxiliary agent, as binding agent containing styrene-the third Olefin(e) acid ester copolymer (Port リ ゾ Le LB-200 (Showa Denko K. K's manufacture, solid constituent 40%, Viscosity 2000mPa.s, pH7.0) (" Port リ ゾ Le " is the registrar of Showa Denko K. K Mark)) emulsion polymer 4 mass parts, as viscosify dispersant by carboxymethyl cellulose (CMC) (1 Viscosity at 23 DEG C of the CMC aqueous solution of quality %: 1100mPa.s) it is dissolved in the CMC of water Aqueous solution (CMC concentration is 2 mass %) 50 mass parts, so add water 5 mass parts carry out kneading, It is fabricated to negative pole slurry.
[making of negative pole]
Copper Foil as thickness 10 μm of collector body is coated with positive pole slurry, so that suppressing Thickness after process becomes 60 μm, is dried 5 minutes with heating plate, then at 110 DEG C at 50 DEG C Under be dried 5 minutes after, use mould press with pressing pressure 2.5t/cm2Suppress, collection is installed Electricity sheet, is thus fabricated to negative pole.
[preparation of electrolyte]
Ethylene carbonate and diethyl carbonate are being mixed with volume ratio 2/3, at the mixed solvent obtained Middle dissolving LiPF6Make the concentration of 1.0mol/L, be prepared as electrolyte.
[making of battery]
Make positive pole and negative pole such as above-mentioned making opposed across the barrier film of polyethylene, put it into aluminium lamination In the container of pressure, in the glove box under argon environment, in the container being placed with above-mentioned electrode in dropping State electrolyte 1.0ml, the thermo-compressed that reduces pressure lamination vessel, it is fabricated to battery.Additionally, should The theoretical capacity of battery is designed as 16.5mAh.
[cell evaluation: initial capacity]
Day ferrum エ レ ッ Network ス charge/discharge testing device is used to be evaluated.After implementing burin-in process, Under the conditions of 25 DEG C, carry out the CC-CV charging of 2 circulations (with 0.2C (with full discharge and recharge in 5 hours Electric current) charge to reach upper voltage limit (4.2V), then charge to through CV with constant voltage (4.2V) Time (1.5 hours)) and CC electric discharge (being discharged to reach lower voltage limit (2.75V) with 0.2C).By 2 times The initial capacity being averagely defined as this battery of capacity during CC electric discharge.
[cell evaluation: initial DC resistance]
After initial capacity measures, under the conditions of 25 DEG C, charge to the 60% of initial capacity with 0.2C Capacity, then carries out CC with 0.2C and discharges 1 minute, the discharge current after measuring 1 second and voltage. Also carry out same CC electric discharge with 0.5C, 1.0C, 2.0C, measure the discharge current after respective 1 second And voltage, draw by each measured value, the slope of near linear is defined as the initial DC electricity of this battery Resistance.
[cell evaluation: charge/discharge cycle characteristics]
Under the conditions of 45 DEG C, repeat the CC-CV charging of 150 circulations (with 2C (with 30 points of full charge and discharges The electric current of electricity) charge to reach upper voltage limit (4.2V), then with constant voltage (4.2V) charge to through The CV time (1.5 hours)) and CC electric discharge (being discharged to become lower voltage limit (2.75V) with 2C) carry out. The charge/discharge cycle characteristics of battery, by trying to achieve capacity dimension holdup, i.e. tries to achieve the electric discharge of the 150th circulation Capacity compares relative to the ratio of the discharge capacity of the 1st circulation.
[embodiment 1]
In the making of positive pole slurry, with planetary-type mixer (プ ラ イ ミ Network ス Co., Ltd. manufactures, Ha イ PVC ス ミ ッ Network ス 2P-03 type) to Resin A 1.25g as resin binder (relative to positive pole Solid constituent 100 mass parts of active substance, the solid constituent of copolymer is 2.5 mass parts) and make For thickening dispersant by carboxymethyl cellulose (hereinafter also referred to " CMC ") (CMC of 1 mass % Aqueous solution is in the viscosity of 23 DEG C: 1100mPa.s) it is dissolved in CMC aqueous solution (the CMC concentration of water It being 2 mass %) (relative to solid constituent 100 mass parts of positive active material, CMC consolidates 20g Body composition is 2.0 mass parts) and as pH regulator, 1,2,3,4-BTCA is dissolved in water 1,2,3,4-butane tetracarboxylic aqueous acid (concentration of 1,2,3,4-BTCA is 10 mass %) 1g (phase For positive active material 100 mass, the solid constituent of 1,2,3,4-BTCA is 0.5 mass parts) Carry out kneading, in them, then add the 20g's as positive active material LiCo1/3Ni1/3Mn1/3O2, as carbon black (acetylene black) 1g of conductive auxiliary agent (relative to positive active material Solid constituent 100 mass parts, be calculated as 5 mass parts with solid constituent), use planetary mixing further Device (プ ラ イ ミ Network ス Co., Ltd. manufacture, Ha イ PVC ス ミ ッ Network ス 2P-03 type) kneading, makes Become anode sizing agent.
[embodiment 2]
In the making of positive pole slurry, using Resin A 1.25g as resin binder, as thickening Dispersant by poly(ethylene oxide) (PEO) (viscosity at 23 DEG C of the PEO aqueous solution of 1 mass %: 12mPa.s) it is dissolved in PEO aqueous solution (PEO concentration the is 10 mass %) 4g of water and as pH The 1,2,3,4-butane tetracarboxylic aqueous acid that 1,2,3,4-BTCA is dissolved in water of regulator (concentration of 1,2,3,4-BTCA is 10 mass %) 1g mixes, and adds water 10g further, With planetary-type mixer (プ ラ イ ミ Network ス Co., Ltd. manufacture, Ha イ PVC ス ミ ッ Network ス 2P-03 type) Kneading, then adds the LiCo of the 20g as positive active material in them1/3Ni1/3Mn1/3O2、 As carbon black (acetylene black) 1g of conductive auxiliary agent, with planetary-type mixer (プ ラ イ ミ Network ス Co., Ltd. Manufacture, Ha イ PVC ス ミ ッ Network ス 2P-03 type) kneading, it is fabricated to anode sizing agent.
[embodiment 3]
In the making of positive pole slurry, using Resin A 1.25g as resin binder, as thickening Dispersant by poly N-ethylene yl acetamide (hereinafter also referred to " PNVA ") (PNVA of 1 mass % Viscosity at 23 DEG C of aqueous solution: 30mPa.s) it is dissolved in PNVA aqueous solution (the PNVA concentration of water It is 10 mass %) 4g and 1,2,3,4-BTCA is dissolved in water as pH regulator 1,2,3,4-butane tetracarboxylic aqueous acid (concentration of 1,2,3,4-BTCA is 10 mass %) 1g is carried out Mixing, adds further water 10g, with planetary-type mixer (プ ラ イ ミ Network ス Co., Ltd. manufactures, Ha イ PVC ス ミ ッ Network ス 2P-03 type) kneading, then add as positive active material in them The LiCo of 20g1/3Ni1/3Mn1/3O2, as carbon black (acetylene black) 1g of conductive auxiliary agent, with planetary mixed Clutch (プ ラ イ ミ Network ス Co., Ltd. manufacture, Ha イ PVC ス ミ ッ Network ス 2P-03 type) kneading, system It is made anode sizing agent.
[embodiment 4]
In the making of positive pole slurry, using Resin A 1.25g as resin binder, as thickening Dispersant by poly N-ethylene yl acetamide and polyacrylic copolymer (copolymerization ratio 70/30) (the most also It is referred to as " PNVA/PAa ") (viscosity at 23 DEG C of the PNVA/PAa aqueous solution of 1 mass %: 450mPa. S) PNVA/PAa aqueous solution (PNVA/PAa concentration is 10 mass %) 4g and the conduct of water it are dissolved in The 1,2,3,4-butane tetracarboxylic aqueous acid that 1,2,3,4-BTCA is dissolved in water of pH regulator (concentration of 1,2,3,4-BTCA is 10 mass %) 1g mixes, and adds water 10g further, With planetary-type mixer (プ ラ イ ミ Network ス Co., Ltd. manufacture, Ha イ PVC ス ミ ッ Network ス 2P-03 type) Kneading, then adds the LiCo of the 20g as positive active material in them1/3Ni1/3Mn1/3O2、 As carbon black (acetylene black) 1g of conductive auxiliary agent, with planetary-type mixer (プ ラ イ ミ Network ス Co., Ltd. Manufacture, Ha イ PVC ス ミ ッ Network ス 2P-03 type) kneading, it is fabricated to anode sizing agent.
[embodiment 5]
In the making of positive pole slurry, as aqueous solution 1,2,3, the 4-butane four of pH regulator Carboxylic acid aqueous solution 2g, in addition, makes positive pole slurry in the way of similarly to Example 1.
[embodiment 6]
In the making of positive pole slurry, as aqueous solution 1,2,3, the 4-butane four of pH regulator Carboxylic acid aqueous solution 0.2g, in addition, makes positive pole slurry in the way of similarly to Example 1.
[embodiment 7]
In the making of positive pole slurry, use citric acid is as pH regulator, and mixing citric acid Aqueous solution (citric acid concentration is 10 mass %) 1g, in addition, in the way of similarly to Example 1 Make positive pole slurry.
[embodiment 8]
In the making of positive pole slurry, use succinic acid is as pH regulator, and mixing succinic acid Aqueous solution (succinic acid concentration is 10 mass %) 1g, in addition, in the way of similarly to Example 1 Make positive pole slurry.
[embodiment 9]
In the making of positive pole slurry, use acetic acid is as pH regulator, and mixing acetic acid is water-soluble Liquid (acetic acid concentration is 10 mass %) 1g, in addition, just makes in the way of similarly to Example 1 Pole slurry.
[embodiment 10]
In the making of positive pole slurry, use methanesulfonic acid is as pH regulator, and mixing methanesulfonic acid Aqueous solution (methanesulfonic acid concentration is 10 mass %) 1g, in addition, in the way of similarly to Example 1 Make positive pole slurry.
[embodiment 11]
In the making of positive pole slurry, use propyl phosphonous acid is as pH regulator, and mixing propyl group Phosphonic acids aqueous solution (propyl phosphonous acid concentration is 10 mass %) 1g, in addition, with similarly to Example 1 Mode make positive pole slurry.
[embodiment 12]
In the making of positive pole slurry, use carbonic acid is as pH regulator, and mixed carbonic acid water water Solution (carbonate concentration is 10 mass %) 1g, in addition, makes in the way of similarly to Example 1 Positive pole slurry.
[comparative example 1]
In the making of positive pole slurry, do not use resin binder, and add water 1.25g, except this it Outward, in the way of similarly to Example 1, positive pole slurry is made.
[comparative example 2]
In the making of positive pole slurry, do not mix 1 as pH regulator, 2,3,4-BTCAs, In addition, in the way of similarly to Example 1, positive pole slurry is made.
[comparative example 3]
In the making of positive pole slurry, do not mix 1 as pH regulator, 2,3,4-BTCAs, In addition, in the way of similarly to Example 2, positive pole slurry is made.
[comparative example 4]
In the making of positive pole slurry, do not mix 1 as pH regulator, 2,3,4-BTCAs, In addition, in the way of similarly to Example 3, positive pole slurry is made.
[comparative example 5]
In the making of positive pole slurry, do not mix 1 as pH regulator, 2,3,4-BTCAs, In addition, in the way of similarly to Example 4, positive pole slurry is made.
[comparative example 6]
In the making of positive pole slurry, mix 1,2,3, the 4-butane tetracarboxylic sour waters as pH regulator Solution 4g (relative to solid constituent 100 mass parts of positive active material, be 2.0 mass parts), removes Outside this, in the way of similarly to Example 1, make positive pole slurry.
[comparative example 7]
In the making of positive pole slurry, as resin binder, it is changed to containing styrene-butadiene The emulsion polymer of rubber ((SBR) solid constituent 40 mass %), in addition, with embodiment 1 Same mode makes positive pole slurry.
[comparative example 8]
In the making of positive pole slurry, as resin binder, it is changed to the emulsion containing SBR and gathers Compound, and do not mix 1 as pH regulator, 2,3,4-BTCAs, in addition, with reality Execute the same mode of example 1 and make positive pole slurry.
[comparative example 9]
In the making of positive pole slurry, by 100 mass parts LiCo1/3Ni1/3Mn1/3O2, as conduction Carbon black (acetylene black) 5 mass parts of auxiliary agent, as binding agent polyvinylidene fluoride (hereinafter also referred to " PVDF ") ((ARKEMA Co., Ltd. manufactures KYNAR, KYNAR is that ARKEMA is public The registered trade mark of department) (concentration of PVDF is 10 mass %)) 10g mixes, and adds N-further Methyl pyrrolidone (NMP) 5g also mixes, and is fabricated to positive pole slurry.
The pH of positive pole slurry, the result of various battery behavior are shown in table 3.
[table 1]
Abbreviation in table is as follows.
NMC:LiCo1/3Ni1/3Mn1/3O2
CMC: carboxymethyl cellulose
PEO: poly(ethylene oxide)
PNVA: poly N-ethylene yl acetamide
PNVA/PAa: poly N-ethylene yl acetamide and polyacrylic copolymer (copolymerization ratio 70/30)
[table 2]
Slightly note in table is as follows.
NMC:LiCo1/3Ni1/3Mn1/3O2
CMC: carboxymethyl cellulose
PEO: poly(ethylene oxide)
PNVA: poly N-ethylene yl acetamide
PNVA/PAa: poly N-ethylene yl acetamide and polyacrylic copolymer (copolymerization ratio 70/30)
SBR: SBR styrene butadiene rubbers
PVDF: polyvinylidene fluoride
*1: containing the emulsion polymer of SBR styrene butadiene rubbers ((SBR) solid constituent 40 mass %)
*2: polyvinylidene fluoride (PVDF) (KYNAR (manufacture of ARKEMA Co., Ltd., KYNAR Registered trade mark for ARKEMA company) (concentration of PVDF is 10 mass %))
[table 3]
According to embodiment 1～4 and comparative example 2～5, the lithium ion secondary battery positive electrode of the present invention is used Slurry is when being not added with pH regulator, and pH is more than 9 deflection alkalescence, on the other hand, by adding Additive, can control its pH at neutral region.Therewith, can press down in lithium rechargeable battery Side reaction processed, and can suppress the positive active material with side reaction may use the lithium of discharge and recharge Consumption, therefore, it can be stated that have both the high capacity characteristics of battery, low resistance characteristic and high charge-discharge and follow Ring sustainment rate characteristic.It is also shown that can use as water solublity with the thickening dispersant of binding agent High molecular cellulose derivative, polyoxyalkylene, polycarboxylate, polycarboxylic acids and polyvinylamide, They can use in the form of homopolymers or copolymers.
According to embodiment 1,5～6, the lithium ion secondary battery positive electrode slurry of the present invention passes through Add appropriate pH regulator, show excellent battery behavior.That is, show relative to positive-active When material 100 mass parts adds the pH regulator of 0.1～1.0 mass parts, show excellent battery behavior. When excessively adding pH adjustment additive such as comparative example 6, it is believed that because the pH of slurry is less than 6.0, Thus producing the corrosion of aluminum collector body, the cementability between active substance and collector body is greatly reduced, battery Performance significantly deteriorates.
Showing according to embodiment 1 and comparative example 6～7, the effect of the pH regulator of positive pole slurry is also Non-can to whole resin binders be suitable for, compared to SBR binding agent, containing ethylenically unsaturated carboxylic acids The resin binder selectivity of the copolymer of ester and ethylenically unsaturated carboxylic acids and aromatic ethenyl compound The high charge-discharge circulation sustainment rate characteristic of ground display battery.
According to embodiment 1～4 and comparative example 9 show, the lithium ion secondary battery positive electrode slurry of the present invention Expect, by adding pH adjustment additive, there is the PVDF binding agent with conventional dicyandiamide solution same Deng or its above effect.

Claims (10)

1. a lithium ion secondary battery positive electrode slurry, it is characterised in that containing (A) positive-active Material, (B) conductive auxiliary agent, (C) resin binder, (D) thickening dispersant, (E) pH regulator and (F) Water,
Described (C) resin binder comprises following copolymer, and described copolymer is ethylenically unsaturated carboxylic acids ester With the copolymer of at least one in ethylenically unsaturated carboxylic acids Yu aromatic ethenyl compound,
Relative to solid constituent 100 mass parts of positive active material, containing of described (E) pH regulator Amount is below more than 0.1 mass parts and 1.0 mass parts, and the pH of slurry is 6.0～8.0 at 23 DEG C.
Lithium ion secondary battery positive electrode slurry the most according to claim 1, described (E) pH adjusts Whole dose is selected from the compound comprising organic acid, mineral acid,
Described organic acid is selected from following compound, and described compound individually or compoundly contains more than 1 Carboxyl, sulfonic group and phosphonate group at least one group,
At least one in phosphoric acid, boric acid and carbonic acid of described mineral acid.
Lithium ion secondary battery positive electrode slurry the most according to claim 1 and 2, described (E) pH Regulator is selected from 1,2,3,4-BTCA, citric acid, succinic acid, acetic acid, methanesulfonic acid, the third sulphur At least one in acid, carbonic acid.
Lithium ion secondary battery positive electrode slurry the most according to claim 1 and 2, described (E) pH Regulator is the pH additive of alkalescence,
The pH of alkalescence additive is used selected from the pH of the pH additive of organic basic, inorganic alkaline Additive,
The pH additive of organic basic is in primary amine, secondary amine, tertiary amine and quaternary ammonium at least one Kind,
The pH additive of inorganic alkaline is selected from ammonia, Lithium hydrate, sodium hydroxide, potassium hydroxide With at least one in calcium hydroxide.
5. according to the lithium ion secondary battery positive electrode slurry according to any one of Claims 1 to 4, Relative to solid constituent 100 mass parts of positive active material, containing more than 0.2 mass parts and 5.0 Described (C) resin binder below mass parts.
6. according to the lithium ion secondary battery positive electrode slurry according to any one of Claims 1 to 5, Described (D) thickening dispersant contains more than one following water soluble polymer, described water soluble polymer Including carboxymethyl cellulose, poly(ethylene oxide), polyacrylic acid, poly-N-vinyl acetamide and propylene Acid and the copolymer of N-vinyl acetamide.
7. a lithium ion secondary battery anode, is to use according to any one of claim 1～6 Lithium ion secondary battery positive electrode slurry and obtain.
8. a manufacture method for lithium ion secondary battery anode, described lithium rechargeable battery is with just Pole possesses the positive electrode active material layer containing positive active material, described manufacturer on positive electrode collector Method has supply lithium ion secondary according to any one of claim 1～6 on described positive electrode collector Anode slurry forms the operation of described positive electrode active material layer.
9. a lithium rechargeable battery, is to use the lithium rechargeable battery described in claim 7 to use Positive pole and obtain.
10. a manufacture method for lithium rechargeable battery, has following operation: prepare claim The operation of the lithium ion secondary battery positive electrode slurry according to any one of 1～6；By described lithium ion two Primary cell positive pole slurry is coated positive electrode collector and is formed positive electrode active material layer to manufacture lithium ion The operation of anode of secondary cell；Assemble the lithium ion two possessing described lithium ion secondary battery anode The operation of primary cell.
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