CN106716687A - Slurry for positive electrode, electrical-storage-device positive electrode, and electrical storage device - Google Patents

Slurry for positive electrode, electrical-storage-device positive electrode, and electrical storage device Download PDF

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Publication number
CN106716687A
CN106716687A CN201580052554.9A CN201580052554A CN106716687A CN 106716687 A CN106716687 A CN 106716687A CN 201580052554 A CN201580052554 A CN 201580052554A CN 106716687 A CN106716687 A CN 106716687A
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positive pole
polymer
storage device
repeat unit
electrical storage
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本多达朗
宫内裕之
前川真希
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JSR Corp
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JSR Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H01M4/04—Processes of manufacture in general
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A slurry for a positive electrode contains polymer particles (A), a lithium-containing olivine phosphate compound (B), and a liquid medium (C). The polymer particles (A) contain a diene polymer having a repeating unit Mc derived from unsaturated carboxylic acid, a repeating unit Md derived from a conjugated diene compound, and a repeating unit Me derived from an aromatic vinyl. The average particle of the polymer particles (A) measures 90-170 nm in diameter.

Description

Positive pole slurry, electrical storage device positive pole and electrical storage device
The reference of related application
This international application is advocated based on the Japanese patent application 2014- in Japan Office's application on the 30th of September in 2014 No. 201467 and the Japanese patent application the 2014-201468th in Japan Office's application on the 30th of September in 2014 it is preferential Power, the full content of Japanese patent application the 2014-201467th and Japanese patent application the 2014-201468th is passed through With reference to introducing this international application.
Technical field
The application is related to positive pole slurry, electrical storage device positive pole and electrical storage device.
Background technology
Used as safe positive active material, with olivine structural phosphate cpd containing lithium, (olivine-type contains Lithium phosphate cpd) get most of the attention.In olivine-type phosphate cpd containing lithium, due to phosphorus and oxygen covalent bonding, therefore, it is thermally-stabilised Property is high, even if also not releasing oxygen at high temperature.
It is 3.4V or so that olivine-type phosphate cpd containing lithium releases voltage due to the occlusion of Li ions, therefore, output Voltage is low.In order to make up the shortcoming, the trial (reference of the characteristic of the periphery materials such as improved electrode adhesive, electrolyte has been carried out Patent document 1~3).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2007-294323 publications
Patent document 2：International Publication WO2010/113940 publications
Patent document 3：Japanese Unexamined Patent Publication 2012-216322 publications
The content of the invention
However, technology disclosed in patent document 1~3 is difficult to fully improve with olivine-type phosphate cpd containing lithium As the charge-discharge characteristic of the electrical storage device of the positive pole of positive active material.The one side of the application is provided can improve electric power storage dress The positive pole slurry of the charge-discharge characteristic put, electrical storage device positive pole and electrical storage device.
The positive pole slurry of the one side of the application contains (A) polymer particle, (B) olivine-type phosphate cpd containing lithium (C) liquid medium, (A) polymer particle contains diene polymer, and the diene polymer has from unsaturation Repeat unit Mc, the repeat unit Md from conjugated diene compound of carboxylic acid and the repeat unit from aromatic ethenyl Me, the average grain diameter of (A) polymer particle is 90~170nm.
If manufacturing electrical storage device positive pole with slurry using the positive pole of the one side of the application and possessing the electrical storage device just The electrical storage device of pole, then can show excellent charge-discharge characteristic.
The positive pole slurry of the another aspect of the application contain (A) polymer, (B) olivine-type phosphate cpd containing lithium and (C) liquid medium, (A) polymer contains diene polymer, and the diene polymer has from unsaturated carboxylic acid Repeat unit Mc, the repeat unit Md from conjugated diene compound and the repeat unit Me from aromatic ethenyl, relatively In content 100 mass parts of (B) olivine-type containing lithium phosphate cpd, the content of (A) polymer is 0.5~1.5 The scope of mass parts.
If manufacturing electrical storage device positive pole with slurry using the positive pole of the another aspect of the application and possessing the electrical storage device The electrical storage device of positive pole, then can show excellent charge-discharge characteristic.
The electrical storage device positive pole of the one side of the application can possess collector and is coated with the surface of the collector Above-mentioned any positive pole slurry and the layer for drying and being formed.If manufactured using the electrical storage device positive pole of the one side of the application Electrical storage device, then can show excellent charge-discharge characteristic.
The electrical storage device positive pole of the another aspect of the application possesses collector and the formation on the surface of above-mentioned collector Layer, the layer contains (A) polymer and (B) olivine-type phosphate cpd containing lithium, and (A) polymer contains diene series polymerization Thing, the diene polymer has the repeat unit Mc from unsaturated carboxylic acid, the repeat unit from conjugated diene compound The Md and repeat unit Me from aromatic ethenyl, relative to content 100 of (B) olivine-type containing lithium phosphate cpd Mass parts, the scope of the content of (A) polymer in 0.5~1.5 mass parts.
If manufacturing electrical storage device using the electrical storage device positive pole of the another aspect of the application, can show excellent Charge-discharge characteristic.
The electrical storage device of the application can possess above-mentioned any electrical storage device positive pole.The electrical storage device of the application being capable of table Reveal excellent charge-discharge characteristic.
Specific embodiment
Presently filed embodiment is illustrated.Should illustrate, the application is not limited to the embodiment party of following records Formula, it should be understood that be additionally included in the various modifications example implemented in the range of the purport for not changing the application.
Should illustrate, " (methyl) acrylic acid~" in this specification is to include " acrylic acid~" and " methacrylic acid~" The concept of both.In addition, "~(methyl) acrylate " be include "~acrylate " and "~methacrylate " this two The concept of person.
In addition, on the mutual binding ability of positive active material (caking property) and positive electrode active material layer and collector Cementability (cementability), from empirically clear and definite its good and bad proportionate relationship for existing substantially with performance.Therefore, this specification In, below, they are included using term as " caking property " sometimes represent.
1. positive pole slurry
The positive pole slurry of present embodiment refers to contain positive active material to be formed on the surface of collector Layer (positive electrode active material layer) and the composition that uses.It is coated with simultaneously by the surface that positive pole slurry is for example coated on collector Dry, positive electrode active material layer can be formed on the surface of collector.
The positive pole slurry of present embodiment contains (A) polymer particle (hereinafter also referred to as " (A) composition "), (B) olive Stone-type phosphate cpd containing lithium (hereinafter also referred to as " (B) composition ") and (C) liquid medium (hereinafter also referred to as " (C) composition "). Hereinafter, the positive pole to present embodiment is described in detail with slurry.
1.1. (A) composition
(A) composition contains diene polymer, the diene polymer have the repeat unit Mc from unsaturated carboxylic acid, Repeat unit Md from the conjugated diene compound and repeat unit Me from aromatic ethenyl.
In positive pole slurry, during (A) composition is dispersed in (C) liquid medium for example in the form of the particle in latex shape.It is logical Cross in the dispersion of latex shape ground, positive pole slurry has good stability, in addition, positive pole slurry coating on the current collector is good It is good.
(A) average grain diameter of composition is preferably in the scope of 90~170nm, more preferably in the scope of 100~165nm.If (A) average grain diameter of composition can fully be adsorbed in the surface of (B) composition in above range, then (A) composition.Thereby, it is possible to Suppress the migration of (A) composition, the uneven optimal distribution that there is few (A) composition in realizing in anode structure.As a result, energy The sufficient adaptation of positive electrode active material layer and collector is enough shown, suppresses the deterioration of the electrical characteristics of electrical storage device.
Should illustrate, the average grain diameter of (A) composition is to use the particle size distribution using light scattering method as measuring principle Device determines size distribution, the small particle of particle diameter population accumulated successively since the size distribution and population it is tired Product frequency reach particle sum in 50% when particle diameter (number average bead diameter, D50) value.
As such particle size distribution device, can for example enumerate Coulter LS230, LS100, LS13 320 (with Upper is Beckman Coulter.Inc systems), FPAR-1000 (great Zhong Electronics Co., Ltd system) etc..In addition, above-mentioned measure side In method, using the water system dispersion (latex) of (A) composition as sample.
Should illustrate, these particle size distribution devices are not only that the primary particle of polymer particle is right as evaluating As, it is also possible to primary particle is condensed and offspring as evaluation object is formed.Therefore, filled by these particle size distributions Put the index that the size distribution for measuring can be used as the dispersity of contained (A) composition in positive pole slurry.
(A) content of composition relative to (B) composition the mass parts of content 100, preferably in the scope of 0.5~1.5 mass parts, Further preferably in the scope of 1~1.5 mass parts.
When the surface coating positive pole slurry of collector and drying form positive electrode active material layer, the positive electrode active material Matter layer contains (A) composition and (B) composition.Here, because (A) composition is compared with (B) composition, electronic conductivity is low, therefore, (A) Composition is typically easy to turn into the resistance components for hindering electronics to be flowed from (B) composition to collector.If (A) composition is relative to (B) The content of the mass parts of content 100 of composition is then difficult to damage the adaptation of collector and positive electrode active material layer in above range, Resistance can be suppressed.As a result, the positive pole for having good electrical characteristics and adaptation concurrently can be made.
1.1.1. the composition of diene polymer
(A) composition contains diene polymer.The diene polymer have the repeat unit Mc from unsaturated carboxylic acid, Repeat unit Md from the conjugated diene compound and repeat unit Me from aromatic ethenyl.
1.1.1.1. the repeat unit Mc from unsaturated carboxylic acid
By having the repeat unit Mc from unsaturated carboxylic acid, the stability of positive pole slurry is carried diene polymer It is high.
As the concrete example of unsaturated carboxylic acid, can enumerate selected from acrylic acid, methacrylic acid, crotonic acid, maleic acid, rich horse More than a kind in the unitary such as acid, itaconic acid or dicarboxylic acids.Particularly preferably it is selected from acrylic acid, methacrylic acid and itaconic acid In more than a kind.
When total repeat unit of diene polymer is set into 100 mass parts, the repeat unit Mc from unsaturated carboxylic acid Content ratio be preferably below 30 mass parts, more preferably 0.3~25 mass parts.If the content ratio of repeat unit Mc exists Above range, then because the dispersion stabilization of (A) composition when positive pole is prepared with slurry is excellent, therefore, it is not likely to produce condensation product. In addition, it is also possible to suppress through when slurry viscosity rising.
1.1.1.2. the repeat unit Md from conjugated diene compound
Diene polymer is by having the repeat unit Md from conjugated diene compound, the bonding of diene polymer Power becomes strong.Therefore, positive electrode active material layer is improved with the caking property of collector.In addition, diene polymer is come from by having The repeat unit Md of conjugated diene compound, caoutchouc elasticity is assigned to diene polymer.Therefore, positive electrode active material layer can Follow the change such as volume contraction, expansion of collector.As a result, the charge-discharge characteristic of electrical storage device can be maintained for a long time.
As conjugated diene compound, for example, can enumerate selected from 1,3-butadiene, 2- methyl isophthalic acids, 3- butadiene, 2, More than a kind in 3- dimethyl -1,3- butadiene, the chloro- 1,3- butadiene of 2- etc..It is special as conjugated diene compound Not preferred 1,3- butadiene.
When total repeat unit is set into 100 mass parts, the content ratio of the repeat unit Md from conjugated diene compound Preferably 30~60 mass parts, more preferably 40~55 mass parts.If the content ratio of repeat unit Md is in above range, Positive electrode active material layer is further improved with the caking property of collector.
1.1.1.3. the repeat unit Me from aromatic ethenyl
, by having the repeat unit Me from aromatic ethenyl, positive pole slurry is containing conductive for diene polymer During imparting agent, (A) composition can be made better with the compatibility of conductivity-imparting agent.
As the concrete example of aromatic ethenyl, can enumerate selected from styrene, AMS, p-methylstyrene, More than a kind in vinyltoluene, chlorostyrene, divinylbenzene etc..It is particularly preferably above-mentioned specific as aromatic ethenyl Styrene in example.
When total repeat unit is set into 100 mass parts, the content ratio of the repeat unit Me from aromatic ethenyl is excellent Elect 10~55 mass parts, more preferably 15~50 mass parts as.If the content ratio of repeat unit Me is in above range, (A) composition has the caking property of appropriateness relative to (B) composition.In addition, the flexibility of the positive electrode active material layer for obtaining, positive pole are lived Property material layer is good to the caking property of collector.
1.1.1.4. other repeat units
Diene polymer can have repeat unit other than the above.As repeat unit other than the above, for example may be used Enumerate the repeat unit Mb from esters of unsaturated carboxylic acids.
When diene polymer has repeat unit Mb from esters of unsaturated carboxylic acids, diene polymer and electrolyte Compatibility is better, can suppress rising of the diene polymer as the internal resistance caused by resistance components in electrical storage device. In addition, positive electrode active material layer and collector that diene polymer exceedingly inhales electrolyte can more effectively be suppressed to result from Caking property reduction.
Above-mentioned esters of unsaturated carboxylic acids is preferably (methyl) acrylate.As the concrete example of (methyl) acrylate, can lift Go out to be selected from (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) acrylic acid isopropyl Ester, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) acrylic acid isoamyl Ester, (methyl) Hexyl 2-propenoate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) acrylic acid N-octyl, (methyl) acrylic acid nonyl ester, (methyl) decyl acrylate, (methyl) dihydroxypropyl methyl esters, (methyl) acrylic acid hydroxyl Base ethyl ester, (methyl) hydroxy butyl acrylate, (methyl) acrylic acid glycol ester, two (methyl) acrylic acid glycol esters, two (first Base) propylene acid propylene glycol ester, three (methyl) acrylic acid trihydroxymethylpropanyl esters, four (methyl) acrylate, pentaerythritols, six (first Base) more than a kind in acrylic acid dipentaerythritol ester, (methyl) allyl acrylate, two (methyl) acrylates etc..
Wherein, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid -2- second are preferably selected from More than a kind in the own ester of base, (methyl) dihydroxypropyl methyl esters and (methyl) Hydroxyethyl Acrylate, particularly preferably it is selected from More than a kind in (methyl) methyl acrylate, (methyl) dihydroxypropyl methyl esters and (methyl) Hydroxyethyl Acrylate.
When total repeat unit is set into 100 mass parts, the repeat unit from esters of unsaturated carboxylic acids of diene polymer The content ratio of Mb is preferably 0~40 mass parts, more preferably 10~30 mass parts.
In addition, as other repeat units, such as can enumerate from α, the repeat unit of alpha, beta-unsaturated nitriles compound.
Used as α, the concrete example of alpha, beta-unsaturated nitriles compound can be enumerated selected from acrylonitrile, methacrylonitrile, α-chloropropene More than a kind in nitrile, α-ethyl acrylonitrile, vinylidene dinitrile etc..Wherein, it is preferably selected from acrylonitrile and methacrylonitrile More than a kind, more preferably acrylonitrile.
In addition, diene polymer can also further have the repeat unit from compound shown below.As The compound, for example, can enumerate the alkane selected from ethene unsaturated carboxylic acids such as (methyl) acrylamide, N hydroxymethyl acrylamides Base acid amides；The vinyl esters of carboxylic acids such as vinyl-acetic ester, vinyl propionate base ester；The acid anhydrides of ethene unsaturated dicarboxylic；Single alkane Base ester；Monoamides；Aminoethyl acrylamide, dimethylaminomethyl Methacrylamide, dimethylaminopropyl metering system More than a kind in aminoalkylamide of the ethene unsaturated carboxylic acid such as acid amides etc..
1.1.2. the synthesis of diene polymer
The synthetic method of diene polymer is not particularly limited, for example, by known emulsion polymerization operation or can incite somebody to action Its appropriately combined operation is easily synthesized.For example can be by using described in No. 4957932 publications of Japanese Patent No. Method etc. is easily synthesized diene polymer.
1.1.3. the physical property of diene polymer
1.1.3.1. counter ion counterionsl gegenions
In order to improve the stability of positive pole slurry, ammonia, alkali metal (lithium, sodium, potassium, rubidium, caesium etc.) hydrogen are preferably previously added The aqueous solution of oxide, inorganic ammonium compounds (ammonium chloride etc.), organic amine compound (monoethanolamine, diethylamide etc.) etc. carries out two The pH regulations of alkene based polymer.
Particularly preferably use selected from least one cation in ammonium ion, sodium ion to the structure as diene polymer The repeat unit Mc from unsaturated carboxylic acid into unit is neutralized and is made salt.If carried out to diene polymer in advance Neutralize, the pH of positive pole slurry is adjusted to 5~13, preferably 6~12 scope can then improve collector and positive electrode active material The caking property of matter layer.
1.1.3.2. tetrahydrofuran (THF) insoluble matter
The THF insoluble matters of diene polymer are preferably more than 80%, more preferably more than 90%.Speculate THF insoluble matters Insoluble matter amount with the electrolyte used in electrical storage device is generally proportionate.Therefore, if THF insoluble matters are in above range, Even if when making electrical storage device and repeating discharge and recharge for a long time, it is also possible to suppress diene polymer in the electrolytic solution molten Go out.
1.1.3.3. transition temperature
The transition temperature of diene polymer can by the means of differential scanning calorimetry according to JIS K7121 determine (DSC) come Determine.Diene polymer preferably only has an endothermic peak in -50~5 DEG C of temperature range.
1.2. (B) composition
As (B) composition contained in the positive pole slurry of present embodiment, for example, can enumerate selected from following formulas (1) institute Show and more than a kind in the oxide containing lithium atom (olivine-type phosphate cpd containing lithium) with olivine-type crystalline texture.
Li1-xM1 x(XO4)·····(1)
(in formula (1), M1It is selected from Mg, Ti, V, Nb, Ta, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Ga, Ge and Sn At least a kind of metal ion, X be selected from Si, S, P and V at least a kind, x be meet 0 ＜ x ＜ 1 relation number)
Should illustrate, the value of the x in above-mentioned formula (1) is according to M1It is with the overall valence mumber of above-mentioned formula (1) with the valence mumber of X The mode of 0 valency is selected.
Electrode potential of the olivine-type containing lithium phosphate cpd shown in above-mentioned formula (1) is according to metallic element M1Species It is different.Therefore, by selecting metallic element M1Species, can suitably set electrode voltage.
As typical example of the olivine-type containing lithium phosphate cpd, LiFePO can be enumerated4、LiCoPO4、 Li0.90Ti0.05Nb0.05Fe0.30Co0.30Mn0.30PO4Deng.Wherein, particularly LiFePO4The iron as raw material of (LiFePO4) Compound is readily available and inexpensively, therefore it is preferred that.
Further, since using as the Fe ion exchanges in the compound of above-mentioned typical example be Co ions, Ni ions or Mn from The compound of son has identical crystal structure with the compound before displacement, has accordingly, as positive active material same Effect.
In positive pole slurry, (B) composition can also have various materials, such as conductive material etc. in its particle surface. The example of typical conductive material is carbon.Such (B) composition can be by public affairs such as Japanese Unexamined Patent Publication 2009-09670 publications The method known is manufactured.
(B) average grain diameter of composition is especially excellent further preferably in 1~25 μm of scope preferably in 1~30 μm of scope It is selected in 1~20 μm of scope.
Positive pole slurry is coated with the surface of collector and dries it, form the operation of film (positive electrode active material layer) In, due to being acted on by surface tension, (below, (A) composition and/or (B) composition move along the thickness direction of film sometimes Also referred to as " migrate ").Specifically, there is the interface (gas with collector opposition side to film in (A) composition and/or (B) composition Liquid/solid interface) mobile trend.
As a result, because the thickness direction for being distributed in film of (A) composition and/or (B) composition becomes uneven, therefore, Sometimes the problems such as producing electrode characteristic deterioration or collector impaired with the caking property of positive electrode active material layer.
For example, oozed out to the gas-solid interface side of positive electrode active material layer as (A) composition that adhesive plays a role (moving OK), collector is relative with the amount of (A) composition at the interface of positive electrode active material layer when tailing off, because electrolyte is to positive-active Being impregnated with for material layer is obstructed, accordingly, there exist the trend of the electrical characteristics deterioration of positive pole.In addition, now, there is collector and positive pole The caking property reduction of active material layer, the trend that positive electrode active material layer is easily peeled off from collector.And then now, due to (A) Composition oozes out, and there is the impaired trend of the flatness on positive electrode active material layer surface.
If however, the average grain diameter of (A) composition is in above-mentioned scope (scope of 90~170nm) and (B) composition Average grain diameter can then suppress the generation of above mentioned problem in above-mentioned scope, can make and have good electrical characteristics and bonding concurrently The positive pole of property.
In addition, if the average grain diameter of (A) composition and (B) composition is in above range, then suction from (A) composition to (B) composition Attached to become firm, dry linting described later is improved.
Here, the average grain diameter of (B) composition is to use the particle size distribution using laser diffractometry as measuring principle to fill Put measure size distribution, the small particle of particle diameter population accumulated successively since the size distribution and population accumulation Frequency for particle sum in 50% when particle diameter (number average bead diameter, D50) value.
As such particle size distribution device using laser diffractometry as measuring principle, for example, can enumerate HORIBA LA-300 series, HORIBA LA-920 series (being above Horiba Ltd's system) etc..In addition, said determination side The sample used in method is after settling (B) composition with pulp centrifuged separation positive pole, to remove sample obtained from its supernatant.
Should illustrate, above-mentioned particle size distribution device be not only by the primary particle of (B) composition as evaluation object, The offspring that primary particle can also be condensed and formed is used as evaluation object.Therefore, by the particle size distribution device The average grain diameter for obtaining can be used as the index of the dispersity of (B) composition contained in positive pole slurry.
1.3. (C) composition
The positive pole slurry of present embodiment contains (C) liquid medium.(C) liquid medium is preferably the water system containing water and is situated between Matter.Water-medium can be the medium being made up of water, it is also possible to the non-water-medium beyond containing water and water.As the non-water system Medium, for example, can enumerate selected from 1 in amide compound, hydrocarbon, alcohol, ketone, ester, amines, lactone, sulfoxide, sulphones etc. More than kind.
(C) when liquid medium contains the non-water-medium beyond water and water, in the mass % of total amount 100 of (C) liquid medium, It is preferred that more than 90 mass % are water, further preferred more than 98 mass % is water.
In addition, the content ratio of non-water-medium contained in water-medium is relative to the mass parts of water-medium 100, preferably Below 10 mass parts, below more preferably 5 mass parts, particularly preferably contain substantially no.
Here, " containing substantially no " refers to not add journey as non-water-medium intentionally in (C) liquid medium Degree, what the non-water-medium or positive pole being inevitably mixed into when can contain making positive pole with slurry were produced after being manufactured with slurry Non- water-medium.
The positive pole slurry of present embodiment, as (C) liquid medium, is difficult to produce environment by using water-medium Impact, operate the security of operator also to uprise.
1.4. other compositions
The positive pole slurry of present embodiment can as needed contain the composition beyond mentioned component.As it is such into Point, can for example enumerate conductivity-imparting agent, non-water-medium, thickener, preservative etc..
1.4.1. conductivity-imparting agent
As the concrete example of above-mentioned conductivity-imparting agent, carbon etc. can be enumerated.Positive pole is being used for lithium ion two by carbon with slurry It is preferred during primary cell (example of electrical storage device).As carbon, for example, can enumerate graphite, activated carbon, acetylene black, oven process charcoal Black, graphite, carbon fiber, fullerene etc..Wherein, preferably acetylene black or furnace black.The use ratio of conductivity-imparting agent is relative In the mass parts of (B) composition 100, below preferably 20 mass parts, more preferably 1~15 mass parts, particularly preferably 2~10 mass Part.
1.4.2. non-water-medium
The positive pole of present embodiment slurry for example from improve its coating from the viewpoint of, can containing have 80~ The non-water-medium of 350 DEG C of normal boiling point.As the concrete example of such non-water-medium, can enumerate selected from N- methyl pyrroles The amide compounds such as pyrrolidone, dimethylformamide, DMAC N,N' dimethyl acetamide；Toluene, dimethylbenzene, n-dodecane, naphthane Deng hydrocarbon；The alcohol such as 2- ethyl -1- hexanols, 1 nonyl alcohol, laruyl alcohol；Methyl ethyl ketone, cyclohexanone, phorone, acetophenone, different Buddhist Your ketone etc. is logical；The esters such as benzyl acetate, isoamyl butyrate, methyl lactate, ethyl lactate, butyl lactate；Ortho-aminotoluene, a toluene The amines such as amine, para-totuidine；The lactones such as gamma-butyrolacton, δ-butyrolactone；The sulfoxide sulfone such as dimethyl sulfoxide (DMSO), sulfolane More than a kind in compound etc..Examined in terms of workability when stability wherein, from (A) composition, coating positive pole slurry etc. Consider, preferably use 1-METHYLPYRROLIDONE.
1.4.3. thickener
The positive pole slurry of present embodiment can contain thickener from from the viewpoint of improving its screening characteristics.As increasing Thick dose of concrete example, can enumerate the cellulosic cpds such as carboxy methyl cellulose, methylcellulose, hydroxy propyl cellulose；On State the ammonium salt or alkali metal salt of cellulosic cpd；The polycarboxylic acids such as poly- (methyl) acrylic acid, modified poly- (methyl) acrylic acid；It is above-mentioned The alkali metal salt of polycarboxylic acids；The polyethenol series (co) polymerization such as polyvinyl alcohol, modified polyvinylalcohol, ethylene-vinyl alcohol copolymer Thing；The water solubility such as saponified of the copolymer of the unsaturated carboxylic acids such as (methyl) acrylic acid, maleic acid and fumaric acid and vinyl esters Polymer etc..Wherein, the alkali metal salt of particularly preferred carboxy methyl cellulose, poly- (methyl) acrylic acid and its alkali metal salt.
As the commercially available product of thickener, for example, can enumerate CMC1120, CMC1150, CMC2200, CMC2280, CMC2450 The alkali metal salt of carboxy methyl celluloses such as (being above DAICEL chemical industry Co. Ltd. system).
When positive pole slurry contains thickener, the total solid content amount of positive pole slurry is set to 100 mass %, thickener Use ratio be preferably below 20 mass %, more preferably 0.1~15 mass %, particularly preferably 0.5~10 mass %.
1.4.4. preservative
The positive pole slurry of present embodiment can contain preservative.By containing preservative, can be used in storage positive pole Suppress the propagation such as bacterium, mould during slurry and produce foreign matter.Further, since the electrical storage device that is manufactured with slurry using positive pole is filled The deterioration of adhesive is inhibited during electric discharge, therefore, it is possible to suppress the reduction of the charge-discharge characteristic of electrical storage device.As preservative, When particularly containing isothiazoline based compound, the effect above is further notable.
As the concrete example of preservative, can enumerate selected from BIT, 2- methyl -4,5- Trimethylene -4- isothiazoline -3- ketone, MIT, 5- chloro-2-methyls -4- Isothiazoline -3- ketone, N- normal-butyl -1,2- benzisothiazole-3-ketones, 2- n-octyl -4- isothiazolines - More than a kind in 3- ketone, DCOIT etc..
Wherein, MIT, 2- n-octyl -4- isothiazolines -3- are preferably selected from More than a kind in ketone, CMIT, 1,2- benzisothiazole-3-ketones etc..
1.5. the manufacture method of positive pole slurry
The positive pole slurry of present embodiment can by by above-mentioned (A) composition, above-mentioned (B) composition, above-mentioned (C) composition and As needed using other compositions mix and manufacture.The order of mixing can suitably set.The mixing of each composition can pass through Known stirring means are carried out, for example, can be mixed using mixer, deaeration machine, ball mill, high pressure homogenizer etc..
At least one of operation in the manufacture (married operation of each composition) of positive pole slurry is preferably entered under reduced pressure OK.Now, can suppress to produce bubble in the positive pole obtained from using positive pole slurry.The degree of decompression is with absolute manometer Preferably 5.0 × 103~5.0 × 105Pa or so.
Do not remained in the mixing for manufacturing positive pole slurry, preferably selecting to stir in positive pole slurry (B) mixer of the degree of the agglomerate of composition and as needed sufficient dispersion condition.
Scattered degree can be measured using hondrometer.It is preferred that being used in positive pole with the condensation product at least above 100 μm Non-existent mode is mixed in slurry.As the mixer for being suitable for such condition, can for example enumerate ball mill, Sand mill, pigment dispersion machine, mixing and kneading machine, ultrasonic dispersing machine, homogenizer, planetary-type mixer, Hobart's mixer etc..
Solid component concentration in the positive pole slurry of present embodiment be (composition beyond solvent in positive pole slurry Total quality relative to positive pole slurry gross mass shared by ratio) be preferably 20~80 mass %, more preferably 30~75 Quality %.
1.6. the characteristic of positive pole slurry
The positive pole slurry de stringiness of present embodiment is preferably 30~80%, more preferably 33~79%.If drawn Silk property is above range, then when positive pole being coated with into formation positive electrode active material layer on the current collector with slurry, be readily obtained fully Levelability.Now, positive electrode active material layer in uniform thickness can be formed.If the thickness using positive electrode active material layer is equal Even positive pole, then can suppress deviation in the face of discharge and recharge reaction, therefore, easily show the electrical storage device characteristic of stabilization.
Should illustrate, above-mentioned " stringiness " can be determined as follows.First, prepare that there is the opening of diameter 5.2mm in bottom Grace cup (helping very much machine material Co. Ltd. system, examine grace flow cup No.5) is examined in portion.In the state of the opening portion that this examines grace cup is closed, To examine grace cup in pour into 40g positive pole slurries.Then, if opening opening portion, positive pole slurry flows out from opening portion.Here, The moment for opening opening portion is set to T0, the moment that the wire drawing of positive pole slurry terminates is set to TA, by the outflow of positive pole slurry The moment of end is set to TBWhen, " stringiness " can be obtained by following formula (2).
Stringiness (%)=((TA- T0)/(TB- T0))×100·····(2)
2. electrical storage device positive pole
The electrical storage device positive pole of present embodiment possesses collector and above-mentioned positive pole is coated with the surface of above-mentioned collector With slurry it is coated and dried and formed layer (positive electrode active material layer).That is, the electrical storage device positive pole is to bond on the current collector Positive electrode active material layer containing above-mentioned (A) composition, above-mentioned (B) composition and other compositions being added as needed on is just Pole.
In the electrical storage device positive pole, collector is excellent with the caking property of positive electrode active material layer.In addition, if using the storage Electric installation positive pole manufactures electrical storage device, and the charge-discharge velocity characteristic as one of electrical storage device characteristic is good.
As long as collector is made up of conductive material and is just not particularly limited.Electrical storage device positive pole is used for lithium ion secondary During battery, for example, can use the metal collectors, particularly preferred aluminium, current collection made of copper such as iron, copper, aluminium, nickel, stainless steel Body.
When electrical storage device positive pole is used for into nickel-hydrogen secondary cell, for example, can use by punch metal, expanding metal, metal The collector of the compositions such as net, foaming metal, net metal fiber sintering body, metal deposition resin plate.
The shape and thickness of collector are not particularly limited, for example the collection of the sheet of 0.001~0.5mm of preferred thickness or so Electric body.
The method that positive pole slurry is coated the surface of collector is not particularly limited.As coating method, for example may be used Suitably to use doctor blade method, dip method, inverse roller method, direct roller method, intagliotype, extrusion, infusion process, spread coating etc..
The coating weight of positive pole slurry is not particularly limited.It (is comprising water to be coated with positive pole slurry and remove liquid medium With the concept of both arbitrarily used non-water-mediums) thickness of positive electrode active material layer that is formed afterwards is preferably 0.005~ The coating weight of the coating weight of 5mm, more preferably 0.01~2mm.
By the thickness of positive electrode active material layer within the above range, electrolyte can be made effectively to penetrate into positive electrode active material Matter layer.As a result, due to the metal ion of the discharge and recharge with positive active material and electrolyte in positive electrode active material layer Give and accept and easily carry out, therefore, it is possible to more reduce the internal resistance of positive pole.
In addition, even if being folded to positive pole, being wound. by the thickness of positive electrode active material layer within the above range And when being processed, positive electrode active material layer is also good with the adaptation of collector, positive electrode active material layer is difficult to from collector Peel off.That is, the electrical storage device positive pole for being rich in flexibility can be obtained.
It is coated with drying means (the removing side of water and arbitrarily used non-water-medium of the film of positive pole slurry Method) it is not particularly limited.For example can be using using warm wind, hot blast, the drying of low wet wind；Vacuum drying；Utilize (remote) infrared The methods such as the drying of the irradiation of line, electron beam etc..
Rate of drying when making the dried coating film of coating positive pole slurry can for example not cause stress to be concentrated Cause positive electrode active material layer cracking or positive electrode active material layer under conditions of collector stripping to remove liquid as quickly as possible The mode of shape medium suitably sets.
After being coated with the dried coating film of positive pole slurry, pressurizeed by electrical storage device positive pole, positive pole can be improved The density of active material layer, is preferably adjusted to scope as shown below by the porosity of density and positive electrode active material layer.
The density of the positive electrode active material layer after pressurization is preferably 1.5~2.5g/cm3, more preferably 1.6~2.4g/cm3, More preferably 1.7~2.2g/cm3, particularly preferably 1.8~2.1g/cm3。
If making the density of positive electrode active material layer for above range, collector and positive electrode active material layer can be obtained Between caking property is good, the electrical storage device positive pole that dry linting is excellent and electrical characteristics are also excellent.
The porosity of the positive electrode active material layer after pressurization is preferably 10~50%, more preferably 15~45%, especially excellent Elect 20~40% as.If making the porosity of positive electrode active material layer for above range, collector can be obtained and lived with positive pole Property material layer between caking property is good, the electrical storage device positive pole that dry linting is excellent and electrical characteristics are also excellent.
In addition, if making the porosity of positive electrode active material layer in above range, electrolyte can be made to be fully infiltrated into positive pole Inside active material layer, positive active material surface is fully contacted with electrolyte.As a result, in positive active material and electrolyte Between giving and accepting for lithium ion become easy, good charge-discharge characteristic can be shown.
As pressure method, for example, can enumerate the methods such as molding, roll-in.The condition of pressurization can set according to the pressurization for using Standby desired value of species, the porosity of positive electrode active material layer and density etc. suitably sets.For the condition pressurizeed, this area Technical staff can lead to too small amount of preliminary experiment and easily set.
Using roll-in method when pressurized conditions can for example be carried out as follows.
The line pressure of roll squeezer is 0.1~10 (t/cm), preferably 0.5~5 (t/cm).
Roll temperature：20~100 DEG C.
The transporting velocity (rotary speed of roller) of electrical storage device positive pole is 1~80m/min, preferably 5~50m/min.
3. electrical storage device
The electrical storage device of present embodiment possesses above-mentioned electrical storage device positive pole, and then, for example contain electrolyte, and have There are the parts such as separator, electrical storage device negative pole.As electrical storage device, for example, can enumerate secondary cell etc..Electrical storage device can be by More solito is manufactured.
As specific manufacture method, for example, can enumerate and enter electrical storage device negative pole and electrical storage device positive pole via separator Row is overlapped, by it is according to the shape of battery (example of electrical storage device) winding, folding etc. and is put into battery case, to battery Container injects electrolyte and the method sealed.The shape of battery can suitably be set as Coin shape, coin shape, piece type, cylinder type, Square, platypelloid type etc..
Electrolyte is in the solution of appropriate solvent by electrolyte dissolution.Electrolyte can be liquid, or Gel.As long as the middle selection of the known electrolyte that electrolyte is used according to the species of positive active material from electrical storage device Effectively show the electrolyte as the function of electrical storage device.
As above-mentioned electrolyte, can suitably be selected in electrolyte known to the technical field from electrical storage device.Electric power storage is filled When being set to lithium rechargeable battery, as electrolyte, known lithium salts can be suitably selected to use, it is specific as its Example, can enumerate LiClO4、LiBF4、LiPF6、LiCF3CO2、LiAsF6、LiSbF6、LiB10Cl10、LiAlCl4、LiCl、LiBr、 LiB(C2H5)4、LiCF3SO3、LiCH3SO3、LiC4F9SO3、Li(CF3SO2)2N, lower fatty acid carboxylic acid lithium etc..
Contained solvent is not particularly limited in electrolyte.As the solvent, for example, can enumerate selected from propylene carbonate, carbon The carbonate products such as sour ethyl, butylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate；Gamma-butyrolacton Deng lactone compound；Trimethoxy-methane, 1,2- dimethoxy-ethanes, Anaesthetie Ether, 2- Ethoxyethanes, tetrahydrofuran, The ether compounds such as 2- methyltetrahydrofurans；More than a kind in sulfoxide compounds such as dimethyl sulfoxide (DMSO) etc..Electrolysis in electrolyte The concentration of matter, preferably 0.5~3.0 mole/L, more preferably 0.7~2.0 mole/L.
The negative pole that the electrical storage device of present embodiment possesses for example possess collector and formed in its surface it is negative Pole active material layer.Negative electrode active material layer contains negative electrode active material.Above-mentioned negative pole for example can be by that will live containing negative pole Property material and for negative pole manufacture negative pole slurry be coated on collector surface and drying and form negative electrode active material layer To manufacture.
Above-mentioned negative electrode active material is not particularly limited, and can suitably select appropriate according to the species of target electrical storage device Negative electrode active material.As negative electrode active material, for example, can enumerate carbon material, silicon materials, the oxide containing lithium atom, leaded Compound, tin compound, arsenic compound, antimonial, aluminium compound etc..
As above-mentioned carbon material, for example, can enumerate amorphous carbon, graphite, native graphite, carbonaceous mesophase spherules (MCMB), drip Blue or green based carbon fiber etc. is used as carbon material known to negative electrode active material.
As above-mentioned silicon materials, for example, elementary silicon, Si oxide, silicon alloy etc. can be enumerated as known in negative electrode active material Silicon materials.In addition, using silicon materials as active material when, preferably and with the active material beyond silicon materials, from lithium Occlusion and the Volume Changes released it is small from the aspect of, preferably and use carbon material.
Negative pole slurry can also contain above-mentioned " 1. positive pole slurry " middle narration in addition to above-mentioned negative electrode active material Adhesive ingredients, liquid medium, conductivity-imparting agent, thickener, preservative etc..
(embodiment 1)
Hereinafter, the application is specifically illustrated based on embodiment, but the application is not limited to these embodiments.It is real " part " and " % " applied in example, comparative example is unless otherwise specified, then quality criteria.
(1) preparation of water system dispersion S1
Can in the lump load the mass parts of water 200, DBSA in the autoclave of temperature adjustment possess mixer The mass parts of sodium 0.9, the mass parts of potassium peroxydisulfate 1.0, the mass parts of sodium hydrogensulfite 0.5, the mass of α-methylstyrenedimer 0.2 Part, the first step polymeric composition shown in " S1 " row in the mass parts of lauryl mercaptan 0.2 and table 1, being warming up to 70 DEG C, to carry out 2 small When polymerisation.
[table 1]
Should illustrate, each composition in table 1 and table described later 2 writes a Chinese character in simplified form respectively following implication.
·MMA：Methyl methacrylate
·HEMA：Methacrylic acid -2- hydroxy methacrylates
·AA：Acrylic acid
·TA：Itaconic acid
·AN：Acrylonitrile
·BD：1,3- butadiene
·ST：Styrene
Here, AA and TA are an example of the repeat unit Mc from unsaturated carboxylic acid, BD is from conjugated diene One example of the repeat unit Md of compound, ST is an example of the repeat unit Me from aromatic ethenyl.MMA、 HEMA and AN are an example of other repeat units.
Confirm polymerization adding rate be more than 80% after, in the state of reaction temperature is maintained into 70 DEG C through 6 hours add Second step polymeric composition shown in the row of " S1 " in table 1.When beginning to pass through 3 hours from the addition of second step polymeric composition The addition mass parts of α-methylstyrenedimer 1.0 and the mass parts of lauryl mercaptan 0.3.
After the addition of second step polymeric composition terminates, temperature is warming up to 80 DEG C, further reaction 2 hours.Polymerisation knot Shu Hou, the addition mass parts of sodium tripolyphosphate 5 (solid constituent conversion), is thus adjusted to 7.5 the pH of latex.Now, acrylic acid It is sodium salt with itaconic acid (example of the repeat unit Mc from unsaturated carboxylic acid).
Then, solid constituent 50% is concentrated into by steam distillation under reduced pressure to residual monomer treatment, is thus obtained Water system dispersion S1 containing 50% (A) polymer particle.(A) polymer particle contained by water system dispersion S1 has table 2 In S1 row shown in composition.
[table 2]
On (A) polymer particle contained in water system dispersion S1, average grain diameter, THF insoluble matters and transformation temperature are determined Degree (Tg).In the measure of average grain diameter, using water system dispersion S1 as measure sample.Measurement result is shown in table 2.
(2) preparation of positive pole slurry and the making of electrical storage device positive pole
Thrown to biaxial type planetary-type mixer (PRIMIX Co. Ltd. systems, trade name " TK HIVIS MIX 2P-03 ") Enter thickener (trade name " CMC1120 ", DAICEL chemical industry Co. Ltd. system) 1 mass parts (solid constituent conversion), Bao Quan LiFePO4 (the LiFePO of Co. Ltd. system4) 100 mass parts, the mass parts of acetylene black 5 and the mass parts of water 68, carry out 1 with 60rpm Hour stirring.Above-mentioned LiFePO4 is crushed using agate mortar, is classified using sieve, thus makes the average grain diameter (D50 values) be 10μm.In addition, an example of the above-mentioned LiFePO4 for positive active material.
Next, input dispersion S1 and preservative CMIT.Dispersion The input amount of S1 is the amount containing 1 mass parts (A) polymer particle.In addition, the input amount of preservative is positive pole slurry total amount In preservative concentration for 100ppm amount.
Then, stir 1 hour and obtain thickener.Add water that solid component concentration is adjusted into 50% in the thickener for obtaining Afterwards, using stirring deaeration machine (Co., Ltd.'s THINKY systems, trade name " Awa Tori RENTARO "), stirred with 200rpm and mixed 2 minutes, with 1800rpm stirrings mixing 5 minutes, further under vacuo (about 5.0 × 103Pa) with 1800rpm stirrings mixing 1.5 Minute, thus prepare positive pole slurry.The positive pole slurry has the composition shown in the row of " embodiment 1 " in table 3.
[table 3]
*1：MIT (ppm)
*2：Kathon (ppm)
*3：CMIT (ppm)
*4：BIT (ppm)
Next, in the way of dried thickness is 100 μm that positive pole slurry produced above is equal using doctor blade method The surface of the collector being made up of the aluminium foil of 30 μm of thickness is coated on evenly, is dried 20 minutes at 120 DEG C.Then, with formation Film (positive electrode active material layer) density be 1.9g/cm3Mode carry out pressure processing using roll squeezer, thus obtain electric power storage Device positive pole.
(3) preparation of negative pole slurry and the making of electrical storage device negative pole
Put into biaxial type planetary-type mixer (PRIMIX Co. Ltd. systems, trade name " TK HIVIS MIX 2P-03 ") Thickener (trade name " CMC2200 ", DAICEL chemical industry Co. Ltd. system) 1 mass parts (solid constituent conversion), conduct are negative The mass parts of graphite 100 (solid constituent conversion) and the mass parts of water 68 of pole active material, with 60rpm stir within 1 hour.
Next, addition 2 mass parts (solid constituent conversion) water system dispersion S1, further stirring 1 hour, is pasted Material.Put into water to the thickener that obtains, after solid constituent is adjusted into 50%, using stirring deaeration machine (Co., Ltd.'s THINKY systems, Trade name " Awa Tori RENTARO "), with 200rpm stirrings mixing 2 minutes, mixing 5 minutes is stirred with 1800rpm, further Under vacuo with 1800rpm stirrings mixing 1.5 minutes, negative pole slurry is thus prepared.
Next, in the way of dried thickness is 80 μm that negative pole slurry produced above is uniform using doctor blade method Be coated on the surface of the collector being made up of the Copper Foil of 20 μm of thickness, 20 minutes dried process are carried out at 120 DEG C.Then, 1.9g/cm is changed into the density of the film (negative electrode active material layer) for being formed3Mode carry out pressure processing using roll squeezer, thus Obtain electrical storage device negative pole.
(4) assembling of lithium ion battery
In the glove box that Ar is replaced as that dew point is less than -80 DEG C, by electrical storage device negative pole punching shaping manufactured as above It is the circle of diameter 15.95mm, the products formed that will be obtained is positioned in 2 pole formula coin battery (precious Izumi Ltd.'s systems, trade name " HS FLAT CELL ") on.
Next, circular (CELGARD plants of the separator being made up of polypropylene perforated membrane for diameter 24mm will be punched Formula commercial firm system, trade name " CELGARD#2400 ") overlap be positioned on electrical storage device negative pole.
And then, after 500 μ L electrolyte are injected in the way of not bringing air into, electrical storage device positive pole manufactured as above is punched The circle of diameter 16.16mm is shaped to, the products formed that will be obtained is overlapped and is positioned on separator, screws down above-mentioned 2 pole formula The exterior body of coin battery is sealed, and thus assembles lithium ionic cell unit (example of electrical storage device).Use herein Electrolyte be to be dissolved with the concentration of 1 mole/L in the solvent of ethylene carbonate/methyl ethyl carbonate=1/1 (mass ratio) LiPF6Solution.
(5) evaluate
The evaluation of (5-1) coating (flatness)
The electrical storage device positive pole made from above-mentioned (2) cuts out the test film of width 12cm × length 12cm.This is tested The size that piece is divided into each grid is 36 grids of 2cm × 2cm, uses film thickness gauge (Mitutoyo systems, DIGIMATIC MICROMETER IP65) determine each grid positive electrode active material layer thickness, calculate the mark of the average value relative to the thickness The ratio (flatness) of quasi- deviation.
Should illustrate, relative to average value standard deviation ratio more than 2% when, it is meant that positive pole is not equal with slurry It is coated with evenly.Under the situation, in the positive pole that large area is coated with positive pole slurry and makes, the positive pole on the surface of collector is formed at The flatness of active material layer is damaged.Therefore, electrical characteristics are uneven in positive pole-face, cannot particularly be shown in a large amount of productions The electrical characteristics of stabilization.
On the other hand, when the ratio relative to the standard deviation of average value is less than 2%, it is meant that positive pole slurry is equal It is coated with evenly.In this case, large area coating positive pole slurry and in the positive pole that makes, be formed at the positive pole on the surface of collector The flatness of active material layer is good.Therefore, electrical characteristics are uniform in positive pole-face, can particularly be shown in a large amount of productions steady Fixed electrical characteristics.From it is such the reasons why consider, the metewand of the coating of positive pole slurry is identified below.Will be based on the evaluation The evaluation result of the flatness of benchmark is shown in table 3.
○：Flatness is less than 2%, well.
×：Flatness is bad more than 2%.
The evaluation of (5-2) dry linting
The electrical storage device positive pole made from above-mentioned (2) cuts out 5 samples of 10cm × 5cm, and they are overlapped.In experiment Commercially available good quality paper is loaded on platform, the stainless (steel) wire of 100 mesh is set thereon.5 samples of overlap are used from the top of net Scissors cuts off.Cut-out is carried out along the short side direction of sample, with 1cm intervals cut-out 9 times.Then, by stainless during observation cut-out Steel mesh trickles down the state of the positive electrode active material powder on good quality paper.Dry linting is evaluated according to the observation result as follows.To comment Valency result is shown in table 3.
○：Dry linting is not observed completely, or observes extremely slight dry linting.Well.
×：It was observed that substantial amounts of dry linting.It is bad.
The evaluation of (5-3) caking property
The electrical storage device positive pole made from above-mentioned (2) cuts out 5 samples of 10cm square, under 120 DEG C of heat pressurization Compression is molded for 5 minutes.Using knife the cut channel up to the depth of collector is cut on the surface of each sample.The cut channel is with 2mm Cut 6 respectively in length and breadth in interval.As a result, forming 25 grids divided in chessboard trellis by cut channel in each sample.
In the surface of each sample, attach adhesive tape in the part of incision cut channel and peel off immediately, count positive electrode active material The quantity of the grid that matter layer is peeled off from Copper Foil.1 above-mentioned operation is implemented to 1 sample (one side), to 5 samples in it is total The number of the grid that the positive electrode active material layer in 125 grid is peeled off is counted, and caking property is evaluated as follows according to the number. Its evaluation result is shown in table 3.
○：The grid that positive electrode active material layer comes off is 0~20, and caking property is good.
×：The grid that positive electrode active material layer comes off is more than 21, and caking property is bad.
The evaluation of (5-4) capacity sustainment rate
For the lithium rechargeable battery of assembling in above-mentioned (4), started to charge up with constant current (1C), continue until voltage Untill 4.2V.Voltage turned into after 4.2 moment, continued to charge with constant voltage (4.2V), and current value is turned into 0.01C Moment terminate (Cut off) as charging.
Then, electric discharge is started with constant current (1C), the moment that voltage turns into 3.0V is terminated into (Cut as electric discharge Off), the 1st discharge capacity of circulation is calculated.50 discharge and recharges are so repeated, the 50th discharge capacity of circulation is calculated.Will be as The 50th discharge capacity of circulation that this is determined is divided by the 1st value of the discharge capacity of circulation as discharge capacity sustainment rate (%), is shown in table 3.When discharge capacity sustainment rate is more than 80%, it can be determined that for good.
The evaluation of (5-5) charge-discharge velocity characteristic
For the lithium rechargeable battery of assembling in above-mentioned (4), started to charge up with constant current (0.2C), continue until electricity Untill pressing to 4.2V.Voltage turned into after the moment of 4.2V, continued to charge with constant voltage (4.2V), and current value is turned into The moment of 0.01C terminates (Cut off) as charging, determines charging capacity during 0.2C.Then, opened with constant current (0.2C) Begin to discharge, the moment that voltage turns into 2.7V is terminated (Cut off) as electric discharge, determine discharge capacity during 0.2C.
Next, for identical lithium rechargeable battery, started to charge up with constant current (3C), continue until voltage into Untill 4.2V.Voltage turned into after the moment of 4.2V, continued to charge with constant voltage (4.2V), and current value is turned into 0.01C Moment terminate (Cut off) as charging, determine 3C when charging capacity.Then, electric discharge is started with constant current (3C), will The moment that voltage turns into 2.7V terminates (Cut off) as electric discharge, determines discharge capacity during 3C.
Then, the ratio (%) of discharge capacity when discharge capacity during calculating 3C is relative to 0.2C, calculates discharge rate Characteristic (%).In addition, the ratio (%) of charging capacity when charging capacity when calculating 3C is relative to 0.2C, calculates charge rate Characteristic (%).
On discharging-rate performance and charge rate characteristic, evaluated by following benchmark.Evaluation result is shown in Table 3.
○：Discharging-rate performance and charge rate characteristic are more than 80%, well.
×：Discharging-rate performance or charge rate characteristic are bad less than 80%.
Should illustrate, " 1C " expression carries out constant to the battery with certain capacitance in the condition determination of the present embodiment The current value that current discharge terminated through electric discharge in 1 hour.For example, " 0.1C " is the current value terminated through electric discharge in 10 hours, " 10C " table Show the current value terminated through electric discharge in 0.1 hour.
The evaluation of (5-6) stringiness
Positive pole to being prepared in above-mentioned (2) evaluates stringiness with slurry.Its evaluation result is shown in table 3.
(embodiment 2~12, comparative example 1~4)
Substantially water system dispersion S2~S13 is prepared as with the water system dispersion S1 in above-described embodiment 1.But, In the preparation of water system dispersion S2~S13, the species and addition of first step polymerizable component and second step polymerizable component As shown in table 1, the species and addition of contained monomer are as shown in table 2 in (A) composition for species and addition.
In addition, the row of " the neutralization ion " in table 2 is recited as in the preparation of water system dispersion of " K ", the hydrogen of equivalent is added Potassium oxide replaces the mass parts of sodium tripolyphosphate 5, and the pH of latex thus is adjusted into 7.5.Now, it is contained in (A) composition to come from The repeat unit Mc of unsaturated carboxylic acid is sylvite.
In addition, the row of " the neutralization ion " in table 2 is recited as " NH4" water system dispersion preparation in, addition equivalent Ammonia replaces the mass parts of sodium tripolyphosphate 5, and the pH of latex is adjusted into 7.5.Now, it is contained from unsaturated carboxylic in (A) composition The repeat unit Mc of acid is ammonium salt.
Average grain diameter, THF insoluble matters and transformation are determined to (A) polymer particle contained in water system dispersion S2~S13 Temperature (Tg).The results are shown in table 2.
In addition, be prepared as with above-described embodiment 1 substantially positive pole slurry, electrical storage device positive pole, negative pole slurry and Electrical storage device negative pole, assembles lithium ion battery.
But, in embodiment 2~12, comparative example 1~4, make the species of (A) composition in positive pole slurry and addition, (B) species and addition of composition, the average grain diameter of (B) composition, the species of (C) composition, the species of other compositions and addition Species and addition described in table 3.In addition, in embodiment 2~12, comparative example 1~4, make (A) in negative pole slurry into It is divided into (A) composition described in table 3.That is, in embodiment 2~12, comparative example 1~4, make in positive pole slurry and negative pole slurry (A) composition difference is identical.
In addition, in embodiment 11, the preparation method for making positive pole slurry is following method.
In water system dispersion S13, residual monomer is removed by steam distillation, pH is adjusted to 7 with NaOH.Connect down Come, 3 times of 1-METHYLPYRROLIDONEs (NMP) of amount of the weight of the latex that addition is obtained make moisture evaporation using evaporator, obtain To the NMP dispersion adhesive compositions of the mass % of solid component concentration 8.
Next, to biaxial type planetary-type mixer (PRIMIX Co. Ltd. systems, trade name " TK HIVIS MIX 2P- 03 ") input adhesive solids composition is NMP dispersion adhesives composition, the Bao Quan of the amount of 1 mass parts (solid constituent conversion) LiFePO4 (the LiFePO of Co. Ltd. system4) 100 mass parts, the mass parts of acetylene black 3 and NMP68 mass parts, carried out with 60rpm Stir within 1 hour, obtain thickener.
Should illustrate, above-mentioned LiFePO4 advances with agate mortar crushing, using sieve classification, thus makes average grain diameter (D50 values) is 10 μm.In addition, an example of the above-mentioned LiFePO4 for positive active material.
Then, after adding NMP that solid component concentration is adjusted into 50 mass % to the thickener for obtaining, stirring deaeration machine is used (Co., Ltd.'s THINKY systems, trade name " Awa Tori RENTARO "), with 200rpm stirrings mixing 2 minutes, is stirred with 1800rpm Mixing 5 minutes is mixed, further under vacuo (about 5.0 × 103Pa) with 1800rpm stirrings mixing 1.5 minutes, positive pole is thus prepared Use slurry.
In addition, in embodiment 12, the preparation method for making positive pole slurry is following method.
400 parts of 10% aqueous sodium carbonate is slowly added into water system dispersion S13, polymer is separated out.By what is separated out After polymer is cleaned with methyl alcohol, further cleaned untill the pH of rinse water turns into less than 8.0 with water.After making cleaning Polymer is vacuum dried 1 day at 50 DEG C and obtains dry polymer.Load the dry polymer 80 for obtaining to separable flask Mass parts and the mass parts of NMP 920, stirring dissolves dry polymer in 2 hours at 50 DEG C, obtains polymer solution.
Next, to biaxial type planetary-type mixer (PRIMIX Co. Ltd. systems, trade name " TK HIVIS MIX 2P- 03 ") input polymer solids composition is the polymer solution of the amount of 1 mass parts, the LiFePO4 of precious Izumi Ltd. (LiFePO4) 100 mass parts, the mass parts of acetylene black 3 and the mass parts of NMP 68, stirring in 1 hour is carried out with 60rpm and obtains thickener. Should illustrate, above-mentioned LiFePO4 advances with agate mortar crushing, using sieve classification, thus makes the average grain diameter (D50 values) be 10μm.In addition, an example of the above-mentioned LiFePO4 for positive active material.
Then, after adding NMP that solid component concentration is adjusted into 50% to the thickener for obtaining, stirring deaeration machine (strain is used Formula commercial firm THINKY systems, trade name " Awa Tori RENTARO "), with 200rpm stirrings mixing 2 minutes, stirred with 1800rpm Mixing 5 minutes, further under vacuo (about 5.0 × 103Pa) with 1800rpm stirrings mixing 1.5 minutes, positive pole use is thus prepared Slurry.
For embodiment 2~12, comparative example 1~4, also evaluated similarly to Example 1.The results are shown in table 3.
(evaluation result of each embodiment and each comparative example)
Contents according to above-mentioned table 3 distinguish, using embodiment 1~12 positive pole slurry when, stringiness, positive pole are special Property (coating, dry linting, caking property) and electrical storage device excellent.
On the other hand, when distinguishing the positive pole slurry using comparative example 1~4, stringiness, anode property and electrical storage device are special In property at least any one when the positive pole slurry using embodiment 1~12 compared with, it is poor.

Claims (8)

1. a kind of positive pole slurry, is situated between containing (A) polymer particle, (B) olivine-type phosphate cpd containing lithium and (C) liquid Matter,
(A) polymer particle contains diene polymer,
The diene polymer has the repeat unit Mc from unsaturated carboxylic acid, the repeat unit from conjugated diene compound The Md and repeat unit Me from aromatic ethenyl,
The average grain diameter of (A) polymer particle is 90~170nm.
2. positive pole slurry according to claim 1, wherein, (B) olivine-type is average containing lithium phosphate cpd Particle diameter is 1~30 μm.
3. a kind of positive pole slurry, containing (A) polymer, (B) olivine-type phosphate cpd containing lithium and (C) liquid medium,
(A) polymer contains diene polymer,
The diene polymer has the repeat unit Mc from unsaturated carboxylic acid, the repeat unit from conjugated diene compound The Md and repeat unit Me from aromatic ethenyl,
Relative to content 100 mass parts of (B) olivine-type containing lithium phosphate cpd, the content of (A) polymer exists The scope of 0.5~1.5 mass parts.
4. the positive pole slurry according to any one of claims 1 to 3, wherein, (B) the olivine-type phosphorylation containing lithium Compound is LiFePO4.
5. the positive pole slurry according to any one of Claims 1 to 4, wherein, the repetition from unsaturated carboxylic acid Unit Mc be selected from sodium ion and potassium ion at least one cation salt.
6. a kind of electrical storage device positive pole, any in possessing collector and being coated with Claims 1 to 5 on the surface of the collector Positive pole slurry and layer that is dry and being formed described in.
7. a kind of electrical storage device positive pole, possesses collector and the layer formed on the surface of the collector,
The layer contains (A) polymer and (B) olivine-type phosphate cpd containing lithium,
(A) polymer contains diene polymer,
The diene polymer has the repeat unit Mc from unsaturated carboxylic acid, the repeat unit from conjugated diene compound The Md and repeat unit Me from aromatic ethenyl,
Relative to content 100 mass parts of (B) olivine-type containing lithium phosphate cpd, the content of (A) polymer exists The scope of 0.5~1.5 mass parts.
8. a kind of electrical storage device, possesses the electrical storage device positive pole described in claim 6 or 7.
CN201580052554.9A 2014-09-30 2015-08-31 Slurry for positive electrode, electrical-storage-device positive electrode, and electrical storage device Pending CN106716687A (en)

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