CN107452938A - Negative plate and lithium ion battery - Google Patents
Negative plate and lithium ion battery Download PDFInfo
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- CN107452938A CN107452938A CN201610382434.1A CN201610382434A CN107452938A CN 107452938 A CN107452938 A CN 107452938A CN 201610382434 A CN201610382434 A CN 201610382434A CN 107452938 A CN107452938 A CN 107452938A
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- negative plate
- acid
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- bisphenol
- ether
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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
- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of negative plate and lithium ion battery.The negative plate includes negative current collector and negative electrode active material layer.The negative electrode active material layer includes negative active core-shell material, binding agent and curing agent.The binding agent includes modified epoxy.The modified epoxy is obtained by introducing the compound containing hydrophilic radical in the compound containing epoxide group.The negative plate of the present invention has higher cohesive force, has good rate capability, the advantage of good cycle using the lithium ion battery of the negative plate.
Description
Technical field
The present invention relates to cell art, more particularly to a kind of negative plate and lithium ion battery.
Background technology
Lithium ion battery has the advantages that high-energy-density, long circulation life, is widely used in movement at present
In phone, notebook computer, digital product.Lithium ion battery by positive plate, negative plate, barrier film and
Electrolyte is formed, and wherein positive plate, negative plate are separated with barrier film, are packaged in aluminum plastic film, injection one
Determine to be fabricated to lithium ion battery by processes such as chemical conversion, agings after electrolyte.Wherein positive electrode active materials
Frequently with cobalt acid lithium, negative active core-shell material is frequently with graphite.
During lithium ion battery use, positive electrode active materials (cobalt acid lithium) deintercalate lithium ions, produce
Lattice variations, but material will not produce obvious Volume Changes in itself.And graphite is as negative active core-shell material,
Lithium-ion embeding is between graphite linings during charging so that away from becoming big, negative plate expands graphite layers；Electric discharge
When lithium ion deviate from from graphite linings, away from diminishing, negative plate thickness reduces graphite layers.Thus lithium from
During sub- circulating battery, volumetric expansion and the cyclic process shunk, graphite are constantly occurring for negative pole graphite
Gradually it can be weakened or be destroyed, bear by bonding for binding agent (being typically SBR emulsion) between particle
Pole piece produces irreversible circulation expansion, causes negative plate super thick, the increase of lithium ion battery thickness, negative pole
Active material also has the higher risk that comes off, and causes lithium ion battery can not use or fail, and lithium from
Sub- battery super thick also can largely influence its performance, particularly with miniaturized electronics, such as
Mobile phone, notebook computer etc..Therefore, it is very to control the negative plate expansion of lithium ion battery in the circulating cycle
Important research direction.
At present, negative plate is mixed with sodium carboxymethylcellulose (CMC) generally using graphite as negative active core-shell material,
Stable sticky slurry is formed by stirring, addition butadiene-styrene rubber (SBR) emulsion, can as binding agent
To obtain negative pole water paste.Gained slurry is coated on collector (copper foil) by way of coating,
It is cold-pressed after drying, then by techniques such as slitting, cut-parts, you can obtain negative plate.In negative pole, CMC is only
Thickening and stable slurry can be played a part of, and SBR plays cementation, the two can not all suppress negative plate
Rebound effect in cyclic process.
In order to suppress expansion of the negative plate in cyclic process, modified SBR conventional at present method, or
Change SBR particle diameter, improve the bonding between bonding and graphite and the collector between graphite particle.So
And improve graphite between or the cohesive force between graphite and collector, usually can only circulation early stage play
Certain effect, during long circulating, still can not suppress the larger expansion of negative plate, cause lithium from
Irreversible expansion in sub- circulating battery.
The content of the invention
In view of problem present in background technology, it is an object of the invention to provide a kind of negative plate and lithium from
Sub- battery, the negative plate have higher cohesive force, are had again using the lithium ion battery of the negative plate
Rate performance is good, the advantage of good cycle.
In order to achieve the above object, in one aspect of the invention, the invention provides a kind of negative plate, its
Including negative current collector and negative electrode active material layer.The negative electrode active material layer includes negative electrode active material
Material, binding agent and curing agent.The binding agent includes modified epoxy.The modified epoxy
Obtained by introducing the compound containing hydrophilic radical in the compound containing epoxide group.
In another aspect of this invention, the invention provides a kind of lithium ion battery, it is included according to this hair
Negative plate described in bright one side.
Relative to prior art, beneficial effects of the present invention are：
The binding agent itself of the present invention has the function of surfactant-like, without using emulsifying agent
Disperse to form stable self-emulsifying systems in water, there is higher bonding using the negative plate of the binding agent
Power, there is good rate capability, the advantage of good cycle using the lithium ion battery of the binding agent.
Embodiment
The following detailed description of the negative plate and lithium ion battery according to the present invention.
Illustrate negative plate according to a first aspect of the present invention first.
Negative plate according to a first aspect of the present invention includes negative current collector and negative electrode active material layer.Institute
Stating negative electrode active material layer includes negative active core-shell material, binding agent and curing agent.The binding agent includes
Modified epoxy.The modified epoxy is contained by being introduced in the compound containing epoxide group
The compound of hydrophilic radical obtains.
In the negative plate of the present invention, modified epoxy resin adhesive itself has surfactant-like
Function, it can disperse to form stable self-emulsifying systems in water without using emulsifying agent, using the bonding
The negative plate of agent has higher cohesive force, has high rate performance using the lithium ion battery of the binding agent
The good, advantage of good cycle.
In the negative plate of the present invention, modified epoxy resin adhesive is due to the characteristic of its own structure, nothing
Emulsifying agent need to be used to disperse to form stable self-emulsifying systems in water, avoid conventional butadiene-styrene rubber
The problem of emulsifying agent (rosin soap solution etc.) must be used in emulsion (SBR), cathode size
Processing characteristics is more stable, is also avoided that emulsifying agent side effect caused by possibility in lithium ion battery.
In the negative plate of the present invention, the main body of modified epoxy resin adhesive is epoxy resin structural, tool
There are more polar group, such as-OH ,-O- etc..- OH has preferable cohesive force to metal base,
Negative active core-shell material can be fixed on the collector of metal, ensure pole piece process and used
Negative active core-shell material will not come off from collector in journey.- O- has preferably compatible with negative active core-shell material
Property, and modified epoxy resin adhesive has certain elasticity, it is ensured that in negative plate process
Toughness, be not in that dry linting etc. is abnormal.
In the negative plate of the present invention, modified epoxy resin adhesive produces crosslinking after coordinating curing agent use
Solidification, the epoxy resin of the crosslinking of formation has higher intensity, in addition to it can fix negative active core-shell material,
Negative active core-shell material can also be suppressed to expand and shrink caused by removal lithium embedded in charge and discharge process, be advantageous to
Reduce the on-reversible cycle expansion in lithium ion battery cyclic process, reduce the thickness of lithium ion battery, prolong
Long life.
In negative plate described according to a first aspect of the present invention, the compound containing epoxide group can
Epoxide group containing two and the above.
In negative plate described according to a first aspect of the present invention, the compound containing epoxide group
Molecular weight can be 200~20000.
In negative plate described according to a first aspect of the present invention, the compound containing epoxide group
Epoxide equivalent can be 80g/mol~1000g/mol.
In negative plate described according to a first aspect of the present invention, in the compound containing hydrophilic radical
Hydrophilic radical be selected from-OH ,-COOH and its salt, acid anhydrides ,-SO3H and its salt, amido ,-CONH-
One or more in (amide groups) ,-N=C=O (NCO) ,-O- (ether).
In negative plate described according to a first aspect of the present invention, the compound choosing containing hydrophilic radical
From polyvinyl alcohol, polyhydric phenols, polyisocyanates, hydrophilic amine, acid amides, amino acid, polyethylene glycol oxide
Glycol, aminobenzoic acid, p-aminobenzene sulfonic acid, benzene sulfonic acid, unrighted acid and its acid anhydrides, binary
One or more in alcohol glycidol ether, poly glycol monomethyl ether.
Wherein, the unrighted acid may be selected from acrylic acid, itaconic acid, oleic acid, linoleic acid, Malaysia
One or more in acid.The unsaturated fat acid anhydrides may be selected from the acid anhydrides of foregoing unrighted acid,
It is preferred that can be maleic anhydride.The polyhydric phenols may be selected from bisphenol-A, Bisphenol F, bisphenol S, hydroquinones,
One or more in resorcinol, catechol.The polyisocyanates may be selected from toluene diisocynate
Ester, methyl diphenylene diisocyanate, 1,5- naphthalene diisocyanates, dimethyl diphenyl diisocyanate,
Oneself two isocyanic acids of hexamethylene diisocyanate, 2,2,4- trimethyls hexamethylene diisocyanate, 2,4,4- trimethyls
Ester, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenation phenylenedimethylidyne
Diisocyanate, IPDI, 4,4'- dicyclohexyl methyl hydride diisocyanates, 1,4- hexamethylenes
Alkane diisocyanate, methylcyclohexane diisocyanate, 1,4- phenylene diisocyanates, norbornane two are sub-
One or more in methyl isocyanate.The hydrophilic amine may be selected from hexamethylene diamine, ethylenediamine, the third two
Amine, butanediamine, diethanol amine, N- aminoethyl piperidines, 2- amino-ethyl -2- carboxyls methane, 2- amino second
One or more in base -2- carboxyls ether, three (methylol) aminomethanes.The acid amides may be selected from propylene
Acid amides, Methacrylamide, DAAM, N hydroxymethyl acrylamide, N- tert-butyl group propylene
Acid amides, NIPA, N- isopropyl acrylamides, dimethylamino-propyl acrylamide,
N, N- DMAA, N, N '-vinyl bisacrylamide, N, N '-methylene-bisacrylamide,
N- (3- dimethylamino-propyls) Methacrylamide, 2- acrylamidos -2- methyl isophthalic acids-propane sulfonic acid, oleic acid
One or more in acid amides, cinnamamide.The dihydric alcohol glycidol ether may be selected from 1,4- butanediols
Diglycidyl ether, ethylene glycol diglycidylether, 1,6 hexanediol diglycidylether, resorcinol
One or more in diglycidyl ether.The molecular weight of the dihydric alcohol glycidol ether can be
50~2000.The poly glycol monomethyl ether may be selected from the monomethyl ether of polyethylene glycol 350, polyethylene glycol 500
Monomethyl ether, Macrogol 600 monomethyl ether, the monomethyl ether of polyethylene glycol 700, polyethylene glycol 2000 list first
One or more in ether.
In negative plate described according to a first aspect of the present invention, the modified epoxy is in water from breast
The particle diameter for changing the emulsion formed is 60nm~600nm.
In negative plate described according to a first aspect of the present invention, the number-average molecular weight of the modified oxygen tree fat
For 10,000~10,000,000.
In negative plate described according to a first aspect of the present invention, the compound choosing containing epoxide group
From diglycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin,
One or more in cycloaliphatic epoxy resin, aliphatic type epoxy resin.
In negative plate described according to a first aspect of the present invention, the compound choosing containing epoxide group
From bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, bisphenol-S diglycidyl ether, season penta
Tetrol glycidol ether, 1,4- butanediol diglycidyl ethers, propylene glycol diglycidylether, benzene diformazan
Sour 2-glycidyl ester, tetrahydrophthalic acid 2-glycidyl ester, hexahydrophthalic acid two shrink sweet
Grease, 4,4 '-MDA four glycidyl group epoxy, triglycidyl group para-aminophenol,
Double (N, the N- 2-glycidyl aminomethyl) hexamethylenes of 1,3-, four glycidols -1,3- double (aminomethyl cyclohexanes),
9,9- bis- [(2,3- glycidoxies) phenyl] fluorenes, 1,4 cyclohexane dimethanol diglycidyl ether, poly- [(2- rings
Oxirane group) -1,2- cyclohexanediols] 2- ethyls -2- (methylol) -1,3- propylene glycols, 3,4- epoxycyclohexyl first
In base -3,4- epoxycyclohexyls formic acid esters, cyanuric acid three-glycidyl epoxy resin, glycolylurea epoxide resin
One or more.
In negative plate described according to a first aspect of the present invention, the compound containing epoxide group
The weight ratio of weight and the compound containing hydrophilic radical is (50%~75%):(25%~75%).
In negative plate described according to a first aspect of the present invention, binding agent and curing agent are with the use of can be with
The structure of three-dimensional netted crosslinking is formed, reaches higher mechanical strength.The specific species of the curing agent is not
It is restricted.I.e. described curing agent is hardener for epoxy resin.Specifically, the curing agent is optional
From aliphatic polyamine, alicyclic polyamine, polyamide, aromatic amine, imidazole curing agent, anhydrides solidification
One or more in agent, amino resins class curing agent and latent curing agent.
In negative plate described according to a first aspect of the present invention, the weight of the binding agent is the negative pole
The 0.5%~3% of the weight of active material.
In negative plate described according to a first aspect of the present invention, the weight of the curing agent is the negative pole
The 0.01%~3% of the weight of active material.
In negative plate described according to a first aspect of the present invention, the negative active core-shell material may be selected from artificial
One or more in graphite, native graphite, hard carbon, silica-base material and tin-based material.
In negative plate described according to a first aspect of the present invention, the negative current collector can be copper foil.
In negative plate described according to a first aspect of the present invention, the negative electrode active material layer may also include
Cathode conductive agent.The cathode conductive agent be selected from acetylene black, conductive black (Super P, Super S,
350G), the one or more in carbon fiber (VGCF), CNT (CNT), Ketjen black.
In negative plate described according to a first aspect of the present invention, the negative electrode active material layer may also include
Cathode size thickener.The cathode size thickener is selected from sodium carboxymethylcellulose, and number-average molecular weight is
The viscosity of 100000~400,000, the 1wt% aqueous solution can be 200~5000mPaS.
Secondly the preparation method of the binding agent of explanation according to a second aspect of the present invention, including step：It will contain
The monomer of reactive functional groups obtains the chemical combination containing epoxide group with the monomer reaction containing epoxide group
Thing；The obtained compound containing epoxide group is reacted with the compound containing hydrophilic radical and is modified
Epoxy resin, complete the preparation of binding agent.
It is described to contain epoxide group in the preparation method of binding agent described according to a second aspect of the present invention
Monomer may be selected from epoxychloropropane.
It is described to contain reactive official in the preparation method of binding agent described according to a second aspect of the present invention
Can the monomer of group be the micromolecular compound containing 2 and above reactive functional groups, the reactive functional
The one kind of group in-OH ,-COOH, acid anhydrides, NCO, amido, amide groups.Wherein,
The micromolecular compound may be selected from bisphenol-A, Bisphenol F, bisphenol S, pentaerythrite, 1,4- butanediols,
Propane diols, phthalic acid, phthalate anhydride, tetrahydrophthalic acid, tetrabydrophthalic anhydride, six
Hydrogen phthalic acid, hexahydrophthalic anhydride, 4,4'- MDAs, para-aminophenol, 1,3-
Diformamide butylcyclohexane, 1,3- diaminomethyls hexamethylene, 9,9- double (4- hydroxyphenyls) fluorenes, 1,4- hexamethylenes two
One kind in methanol.
In the preparation method of binding agent described according to a second aspect of the present invention, the change containing epoxide group
Compound also can be directly commercially available.
Next the lithium ion battery of explanation according to a third aspect of the present invention, it is included according to the present invention first
Negative plate, positive plate, barrier film and electrolyte described in aspect.
In lithium ion battery described according to a third aspect of the present invention, the positive plate includes anode collection
Body and the positive electrode active material layer on plus plate current-collecting body.The plus plate current-collecting body is aluminium foil.It is described just
Pole active material layer composition is as follows, by weight, positive electrode active materials:Positive conductive agent:Positive pole bonds
Agent=(92%~100%):(0%~4%):(0%~4%).
In lithium ion battery described according to a third aspect of the present invention, the positive electrode active materials are selected from cobalt
Sour lithium (LiCoO2), LiMn2O4, LiFePO4, one kind in nickel cobalt manganese metal oxide (NCM)
It is or several.The positive conductive agent is selected from acetylene black, conductive black (Super P, Super S, 350G
Deng), carbon fiber (VGCF), CNT (CNT), the one or more in Ketjen black.Institute
State positive electrode binder and be selected from Kynoar (PVdF), number-average molecular weight can be 600,000~1,200,000.
Below by way of specific embodiment, the present invention is described in detail, and these embodiments are only intended to illustrate
The present invention, and the invention is not restricted to following examples.It is every technical solution of the present invention is modified or
Equivalent substitution, without departing from the spirit and scope of technical solution of the present invention, the guarantor in the present invention all should be covered
Protect in scope.
Embodiment 1
(1) preparation of modified epoxy
Bisphenol-A and epoxychloropropane, NaOH are added to reactor, normal-temperature reaction 3h, are warming up to
60 DEG C of reaction 3h, bisphenol A diglycidyl ether is obtained after washing, being dehydrated.Wherein, bisphenol-A two
The molecular weight of glycidol ether is 340.
Above-mentioned bisphenol A diglycidyl ether, bisphenol-A, hydroquinones, 1,4- butanediols two are shunk sweet
Oily ether (molecular weight 202) adds reactor, while adds 0.15% (weight fraction) triphenylamine
As catalyst, 200 DEG C of reaction 8h are heated to, 100 DEG C is cooled to, it is single to add polyethylene glycol 500
Methyl ether, 10h is reacted at 100 DEG C, complete the preparation of modified epoxy.Wherein, the modified ring
The particle diameter for the emulsion that oxygen tree fat is formed in water is 170nm.The number-average molecular weight of the modified oxygen tree fat is about
For 1,850,000.Fraction meter by weight, bisphenol A diglycidyl ether:1,4- butanediol diglycidyl ethers:
Bisphenol-A:Hydroquinones:Monomethyl ether=60% of polyethylene glycol 500:20%:5%:5%:10%.
(2) preparation of negative plate
Fraction meter by weight, by 95.0% negative active core-shell material Delanium, 2.0% cathode size stabilizer
Sodium carboxymethylcellulose, 1.0% cathode conductive agent Super P, 1.95% modified epoxy, 0.05%
Latent curing agent (ADK, EH-3293S), add in distilled water and stir, coated in negative pole collection
On the two sides of fluid copper foil (thickness is 10 μm), by drying, roll-in, cutting, welding negative electrode lug
After obtain negative plate.
(3) preparation of positive plate
Fraction meter by weight, by 96.0% positive electrode active materials LiCoO2, 2.0% positive electrode binder gather inclined fluorine
Ethene, 2.0% positive conductive agent Super P are added in NMP, are stirred, coated in plus plate current-collecting body
On the two sides of aluminium foil (thickness is 14 μm), after drying, roll-in, cutting, welding anode ear
To positive plate.
(4) preparation of electrolyte
Electrolyte includes organic solvent and lithium salts, and organic solvent is diethyl carbonate, dimethyl carbonate, carbon
The mixture of vinyl acetate, the volume ratio of three kinds of organic solvents is 1:1:1, lithium salts LiPF6, concentration is
1mol/L。
(5) preparation of lithium ion battery：By positive plate, negative plate and barrier film, (polyethylene is isolated
Film, 14 μm of thickness) battery core is wound into, battery core is placed in aluminum plastic film, baking water removal, reinjects electricity
Liquid is solved, battery core is melted into and aging, obtains corresponding lithium ion battery.
Embodiment 2
The preparation process of lithium ion battery is same as Example 1, and difference is：
(1) preparation of modified epoxy
Tetrahydrophthalic acid and epoxychloropropane, NaOH are added to reactor, normal-temperature reaction 3h,
60 DEG C of reaction 3h are warming up to, tetrahydrophthalic acid 2-glycidyl ester is obtained after washing, being dehydrated.
Wherein, the molecular weight of tetrahydrophthalic acid 2-glycidyl ester is 282.
By above-mentioned tetrahydrophthalic acid 2-glycidyl ester, bisphenol-A, hydroquinones, 1,4- butanediols
Diglycidyl ether adds reactor, while adds 0.15% (weight fraction) triphenylamine as catalysis
Agent, 200 DEG C of reaction 8h are heated to, 100 DEG C is cooled to, adds the monomethyl ether of polyethylene glycol 500,
10h is reacted at 100 DEG C, completes the preparation of modified epoxy.Wherein, the modified epoxy is in water
The particle diameter of the emulsion of middle formation is 190nm.The number-average molecular weight of the modified oxygen tree fat is about 2,010,000.
Fraction meter by weight, tetrahydrophthalic acid 2-glycidyl ester:1,4- butanediol diglycidyl ethers:Bis-phenol
A:Hydroquinones:Monomethyl ether=60% of polyethylene glycol 500:20%:5%:5%:10%.
Embodiment 3
The preparation process of lithium ion battery is same as Example 1, and difference is：
(1) preparation of modified epoxy
Para-aminophenol and epoxychloropropane, NaOH are added to reactor, normal-temperature reaction 3h, heating
To 60 DEG C of reaction 3h, triglycidyl group para-aminophenol is obtained after washing, being dehydrated.Wherein, three
The molecular weight of glycidyl para-aminophenol is 277.
Above-mentioned triglycidyl group para-aminophenol, bisphenol-A, hydroquinones, 1,4- butanediols two are contracted
Water glycerin ether adds reactor, while adds 0.15% (weight fraction) triphenylamine as catalyst,
200 DEG C of reaction 8h are heated to, 100 DEG C is cooled to, the monomethyl ether of polyethylene glycol 500 is added, 100
10h is reacted at DEG C, completes the preparation of modified epoxy.Wherein, the modified epoxy is in water
The particle diameter of the emulsion of formation is 170nm.The number-average molecular weight of the modified oxygen tree fat is about 2,130,000.Press
Weight fraction meter, triglycidyl group para-aminophenol:1,4- butanediol diglycidyl ethers:Bisphenol-A:To benzene
Diphenol:Monomethyl ether=60% of polyethylene glycol 500:20%:5%:5%:10%.
Embodiment 4
The preparation process of lithium ion battery is same as Example 1, and difference is：
(1) preparation of modified epoxy
Bisphenol-A and epoxychloropropane, NaOH are added to reactor, normal-temperature reaction 3h, are warming up to
60 DEG C of reaction 3h, bisphenol A diglycidyl ether is obtained after washing, being dehydrated.Wherein, bisphenol-A two
The molecular weight of glycidol ether is 340.
Above-mentioned bisphenol A diglycidyl ether, bisphenol-A, p-aminobenzoic acid, 1,4- butanediols two are contracted
Water glycerin ether adds reactor, while adds 0.15% (weight fraction) triphenylamine as catalyst,
200 DEG C of reaction 8h are heated to, 100 DEG C is cooled to, the monomethyl ether of polyethylene glycol 500 is added, 100
10h is reacted at DEG C, completes the preparation of modified epoxy.Wherein, the modified epoxy is in water
The particle diameter of the emulsion of formation is 200nm.The number-average molecular weight of the modified oxygen tree fat is about 1,970,000.Press
Weight fraction meter, bisphenol A diglycidyl ether:1,4- butanediol diglycidyl ethers:Bisphenol-A:To amino
Benzoic acid:Monomethyl ether=60% of polyethylene glycol 500:20%:5%:5%:10%.
Embodiment 5
The preparation process of lithium ion battery is same as Example 1, and difference is：
(1) preparation of modified epoxy
Bisphenol-A and epoxychloropropane, NaOH are added to reactor, normal-temperature reaction 3h, are warming up to
60 DEG C of reaction 3h, bisphenol A diglycidyl ether is obtained after washing, being dehydrated.Wherein, bisphenol-A two
The molecular weight of glycidol ether is 340.
Above-mentioned bisphenol A diglycidyl ether, hexamethylene diamine, hydroquinones, 1,4- butanediols two are shunk sweet
Oily ether adds reactor, while adds 0.15% (weight fraction) triphenylamine as catalyst, heating
To 200 DEG C of reaction 8h, 100 DEG C are cooled to, the monomethyl ether of polyethylene glycol 500 is added, at 100 DEG C
10h is reacted, completes the preparation of modified epoxy.Wherein, the modified epoxy is formed in water
The particle diameter of emulsion be 180nm.The number-average molecular weight of the modified oxygen tree fat is about 2,010,000.By weight
Fraction meter, bisphenol A diglycidyl ether:1,4- butanediol diglycidyl ethers:Hexamethylene diamine:Hydroquinones:It is poly-
Monomethyl ether=60% of ethylene glycol 500:20%:5%:5%:10%.
Embodiment 6
The preparation process of lithium ion battery is same as Example 1, and difference is：
(1) preparation of modified epoxy
Bisphenol-A and epoxychloropropane, NaOH are added to reactor, normal-temperature reaction 3h, are warming up to
60 DEG C of reaction 3h, bisphenol A diglycidyl ether is obtained after washing, being dehydrated.Wherein, bisphenol-A two
The molecular weight of glycidol ether is 340.
By above-mentioned bisphenol A diglycidyl ether, bisphenol-A, hydroquinones, resorcinol 2-glycidyl
Ether (molecular weight 222) adds reactor, while adds 0.15% (weight fraction) triphenylamine and make
For catalyst, 200 DEG C of reaction 8h are heated to, 100 DEG C is cooled to, adds 500 single first of polyethylene glycol
Ether, 10h is reacted at 100 DEG C, complete the preparation of modified epoxy.Wherein, the modified epoxy
The particle diameter for the emulsion that resin is formed in water is 170nm.The number-average molecular weight of the modified oxygen tree fat is about
1770000.Fraction meter by weight, bisphenol A diglycidyl ether:Resorcinolformaldehyde resin:Bis-phenol
A:Hydroquinones:Monomethyl ether=60% of polyethylene glycol 500:20%:5%:5%:10%.
Embodiment 7
The preparation process of lithium ion battery is same as Example 1, and difference is：
(1) preparation of modified epoxy
Bisphenol-A and epoxychloropropane, NaOH are added to reactor, normal-temperature reaction 3h, are warming up to
60 DEG C of reaction 3h, bisphenol A diglycidyl ether is obtained after washing, being dehydrated.Wherein, bisphenol-A two
The molecular weight of glycidol ether is 340.
Above-mentioned bisphenol A diglycidyl ether, bisphenol-A, hydroquinones, 1,4- butanediols two are shunk sweet
Oily ether adds reactor, while adds 0.05% (weight fraction) triphenylamine as catalyst, heating
To 200 DEG C of reaction 2h, 100 DEG C are cooled to, the monomethyl ether of polyethylene glycol 500 is added, at 100 DEG C
10h is reacted, completes the preparation of modified epoxy.Wherein, the modified epoxy is formed in water
The particle diameter of emulsion be 155nm.The number-average molecular weight of the modified oxygen tree fat is about 1.2 ten thousand.By weight
Fraction meter, bisphenol A diglycidyl ether:1,4- butanediol diglycidyl ethers:Bisphenol-A:Hydroquinones:It is poly-
Monomethyl ether=60% of ethylene glycol 500:20%:5%:5%:10%.
Embodiment 8
The preparation process of lithium ion battery is same as Example 1, and difference is：
(1) preparation of modified epoxy
Bisphenol-A and epoxychloropropane, NaOH are added to reactor, normal-temperature reaction 3h, are warming up to
60 DEG C of reaction 3h, bisphenol A diglycidyl ether is obtained after washing, being dehydrated.Wherein, bisphenol-A two
The molecular weight of glycidol ether is 340.
Above-mentioned bisphenol A diglycidyl ether, bisphenol-A, hydroquinones, 1,4- butanediols two are shunk sweet
Oily ether adds reactor, while adds 0.5% (weight fraction) triphenylamine as catalyst, is heated to
200 DEG C of reaction 24h, are cooled to 100 DEG C, add the monomethyl ether of polyethylene glycol 500, anti-at 100 DEG C
10h is answered, completes the preparation of modified epoxy.Wherein, the modified epoxy is formed in water
The particle diameter of emulsion is 210nm.The number-average molecular weight of the modified oxygen tree fat is about 10,000,000.By weight
Fraction meter, bisphenol A diglycidyl ether:1,4- butanediol diglycidyl ethers:Bisphenol-A:Hydroquinones:It is poly-
Monomethyl ether=60% of ethylene glycol 500:20%:5%:5%:10%.
Comparative example 1
The preparation process of lithium ion battery is same as Example 1, and difference is：
Without the preparation of modified epoxy, and the preparation process of negative plate is fraction meter by weight, will
95.0% negative active core-shell material Delanium, 2.0% cathode size stabilizer sodium carboxymethylcellulose, 1.0%
Cathode conductive agent Super P, 2.0% negative electrode binder are SBR emulsion (Japanese Zeon, BM400)
Add in distilled water and stir, on the two sides coated in negative current collector copper foil (thickness is 10 μm),
Negative plate is obtained after drying, roll-in, cutting, welding negative electrode lug.
Next the performance test of explanation lithium ion battery.
(1) the cohesive force test of negative plate
Before soaking electrolyte：Negative plate is cut into long 100mm, wide 10mm rectangle.Take one wide
25mm stainless steel plate is spent, patch double faced adhesive tape (width 11mm), the negative plate cut out is pasted not
On the double faced adhesive tape to become rusty on steel plate, rolled back and forth three times on the surface of negative plate with 2000g pressure rollers
(300mm/min).Negative plate 180 degree is bent, peels off 25mm manually, the sample is fixed on
On testing machine, release surface is set to be consistent with the testing machine line of force, testing machine is continuously peeled off with 300mm/min,
Obtained peel force curve, the average of steady section is taken as peeling force F0, then be tested negative plate bonding
Power is：F=F0/ 0.01=100F0。
After soaking electrolyte：Negative plate is cut into long 100mm, wide 10mm rectangle, is immersed in electricity
Solve in liquid (identical with the electrolyte in lithium ion battery preparation process), be placed in dry environment (relative
Humidity<5%) soak at room temperature 24 hours, take out makes it be volatilized naturally in dry environment afterwards, treats
The organic solvent on negative plate surface is evaporated completely, and tests negative plate cohesive force.Method of testing and cohesive force meter
Calculation method is same as above.
(2) the high rate performance test of lithium ion battery
Under normal temperature, lithium ion battery is cut with 0.5C constant-current charges to 4.35V, constant-voltage charge to 0.05C
Only.0.5C constant-current discharges end to 3.0V, discharge capacity are recorded, using this capacity as 100%.
Under normal temperature, lithium ion battery is cut with 1.0C constant-current charges to 4.35V, constant-voltage charge to 0.05C
Only.0.5C constant-current discharges end to 3.0V, record discharge capacity, calculate percentage.
Under normal temperature, lithium ion battery is cut with 1.5C constant-current charges to 4.35V, constant-voltage charge to 0.05C
Only.0.5C constant-current discharges end to 3.0V, record discharge capacity, calculate percentage.
Under normal temperature, lithium ion battery is cut with 2.0C constant-current charges to 4.35V, constant-voltage charge to 0.05C
Only.0.5C constant-current discharges end to 3.0V, record discharge capacity, calculate percentage.
(3) the cycle performance test of lithium ion battery
Under normal temperature, lithium ion battery is cut with 0.5C constant-current charges to 4.35V, constant-voltage charge to 0.05C
Only, ended afterwards with 0.5C constant-current discharges to 3.0V, this is cyclic process first, and record circulates first
Discharge capacity and first circulate after lithium ion battery thickness.Using the discharge capacity that circulates first as
100%, the residual capacity after the multiple circulation of record lithium ion battery.With lithium ion battery after circulating first
Thickness is 100%, the thickness swelling after the multiple circulation of record lithium ion battery.
The cohesive force test result of the negative plate of table 1
The high rate performance test result of the lithium ion battery of table 2
| 0.5C | 1.0C | 1.5C | 2.0C | |
| Comparative example 1 | 100.0% | 91.5% | 73.9% | 51.3% |
| Embodiment 1 | 100.0% | 92.6% | 78.2% | 63.1% |
| Embodiment 2 | 100.0% | 92.3% | 77.9% | 67.9% |
| Embodiment 3 | 100.0% | 91.9% | 77.6% | 59.3% |
| Embodiment 4 | 100.0% | 92.5% | 77.0% | 65.0% |
| Embodiment 5 | 100.0% | 92.9% | 76.5% | 66.9% |
| Embodiment 6 | 100.0% | 92.5% | 77.3% | 60.2% |
| Embodiment 7 | 100.0% | 91.8% | 77.0% | 58.8% |
| Embodiment 8 | 100.0% | 92.6% | 78.1% | 70.2% |
The cycle performance test result of the lithium ion battery of table 3
The negative plate that can be seen that the present invention from the test result of above-mentioned table 1 to table 3 has higher glue
Power is tied, there is good rate capability, the advantage of good cycle using the lithium ion battery of the negative plate.
Claims (10)
1. a kind of negative plate, including：
Negative current collector；And
Negative electrode active material layer, including negative active core-shell material, binding agent and curing agent；
Characterized in that,
The binding agent includes modified epoxy；
The modified epoxy contains hydrophilic radical by being introduced in the compound containing epoxide group
Compound obtain.
2. negative plate according to claim 1, it is characterised in that the change containing epoxide group
The molecular weight of compound is 200~20000, and the epoxide equivalent of the compound containing epoxide group is
80g/mol~1000g/mol.
3. negative plate according to claim 1, it is characterised in that the change containing hydrophilic radical
Hydrophilic radical in compound is selected from-OH ,-COOH and its salt, acid anhydrides ,-SO3H and its salt, amido,
One or more in amide groups ,-N=C=O, ether.
4. the negative plate according to claim 1 or 3, it is characterised in that described to contain hydrophilic radical
Compound be selected from polyvinyl alcohol, polyhydric phenols, polyisocyanates, hydrophilic amine, acid amides, amino acid,
Polyoxyethylene glycol, aminobenzoic acid, p-aminobenzene sulfonic acid, benzene sulfonic acid, unrighted acid and its
One or more in acid anhydrides, dihydric alcohol glycidol ether, poly glycol monomethyl ether.
5. negative plate according to claim 1, it is characterised in that the number of the modified epoxy
Average molecular weight is 10,000~10,000,000.
6. negative plate according to claim 1, it is characterised in that the change containing epoxide group
Compound is selected from diglycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type ring
One or more in oxygen tree fat, cycloaliphatic epoxy resin, aliphatic type epoxy resin.
7. negative plate according to claim 6, it is characterised in that the change containing epoxide group
Compound be selected from bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, bisphenol-S diglycidyl ether,
Pentaerythrite glycidol ether, 1,4- butanediol diglycidyl ethers, propylene glycol diglycidylether, benzene
Dicarboxylic acid diglycidyl ester, tetrahydrophthalic acid 2-glycidyl ester, hexahydrophthalic acid two contract
Water glyceride, 4,4 '-MDA four glycidyl group epoxy, triglycidyl group p-aminophenyl
Double (N, the N- 2-glycidyl aminomethyl) hexamethylenes of phenol, 1,3-, double (the aminomethyl hexamethylenes of four glycidol -1,3-
Alkane), 9,9- bis- [(2,3- glycidoxies) phenyl] fluorenes, 1,4 cyclohexane dimethanol diglycidyl ether, poly- [(2-
Oxyranyle) -1,2- cyclohexanediols] 2- ethyls -2- (methylol) -1,3- propylene glycols, 3,4- epoxycyclohexyls
Methyl -3,4- epoxycyclohexyls formic acid esters, cyanuric acid three-glycidyl epoxy resin, glycolylurea epoxide resin
In one or more.
8. negative plate according to claim 1, it is characterised in that the change containing epoxide group
The weight ratio of the weight of compound and the compound containing hydrophilic radical is (50%~75%):
(25%~75%).
9. negative plate according to claim 1, it is characterised in that
The weight of the binding agent is the 0.5%~3% of the weight of the negative active core-shell material；
The weight of the curing agent is the 0.01%~3% of the weight of the negative active core-shell material.
10. a kind of lithium ion battery, it is characterised in that including according to any one of claim 1-9
Negative plate.
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| CN110484164A (en) * | 2019-07-18 | 2019-11-22 | 河南平煤国能锂电有限公司 | A kind of compound negative electrode of lithium ion battery binder |
| CN110767956A (en) * | 2019-11-02 | 2020-02-07 | 河南电池研究院有限公司 | Method for stripping lithium ion battery electrode plate material and current collector |
| CN111509191A (en) * | 2020-04-24 | 2020-08-07 | 中科(马鞍山)新材料科创园有限公司 | Negative electrode slurry, preparation method thereof and lithium ion battery |
| CN112909432A (en) * | 2021-01-26 | 2021-06-04 | 东莞维科电池有限公司 | High-hardness lithium ion battery |
| CN114883563A (en) * | 2022-05-11 | 2022-08-09 | 厦门海辰新能源科技有限公司 | Battery slurry, positive pole piece, negative pole piece and lithium battery |
| CN116111100A (en) * | 2023-04-12 | 2023-05-12 | 深圳好电科技有限公司 | Lithium ion battery negative electrode material, preparation method thereof and lithium ion battery |
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Cited By (9)
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| CN110484164A (en) * | 2019-07-18 | 2019-11-22 | 河南平煤国能锂电有限公司 | A kind of compound negative electrode of lithium ion battery binder |
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| CN111509191A (en) * | 2020-04-24 | 2020-08-07 | 中科(马鞍山)新材料科创园有限公司 | Negative electrode slurry, preparation method thereof and lithium ion battery |
| CN112909432A (en) * | 2021-01-26 | 2021-06-04 | 东莞维科电池有限公司 | High-hardness lithium ion battery |
| CN114883563A (en) * | 2022-05-11 | 2022-08-09 | 厦门海辰新能源科技有限公司 | Battery slurry, positive pole piece, negative pole piece and lithium battery |
| CN114883563B (en) * | 2022-05-11 | 2023-09-08 | 厦门海辰储能科技股份有限公司 | Battery slurry, positive electrode plate, negative electrode plate and lithium battery |
| CN116111100A (en) * | 2023-04-12 | 2023-05-12 | 深圳好电科技有限公司 | Lithium ion battery negative electrode material, preparation method thereof and lithium ion battery |
| CN116111100B (en) * | 2023-04-12 | 2023-09-19 | 深圳好电科技有限公司 | Lithium ion battery negative electrode material, preparation method thereof and lithium ion battery |
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