CN108933260A - Water-soluble electrode binder, electrode plate, preparation method of electrode plate and electrochemical energy storage device - Google Patents
Water-soluble electrode binder, electrode plate, preparation method of electrode plate and electrochemical energy storage device Download PDFInfo
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- CN108933260A CN108933260A CN201710367891.8A CN201710367891A CN108933260A CN 108933260 A CN108933260 A CN 108933260A CN 201710367891 A CN201710367891 A CN 201710367891A CN 108933260 A CN108933260 A CN 108933260A
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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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- 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
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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
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Abstract
The application provides a water-soluble electrode binder, an electrode plate, a preparation method of the electrode plate and an electrochemical energy storage device. The water-soluble electrode binder is prepared from a water-soluble polymer and a cross-linking agent. The water-soluble polymer contains-COOH functional groups. The cross-linking agent is one or more of an amine monomer compound containing 2 or more than 2 amino groups or imino groups and an amine polymer formed by homopolymerization or copolymerization of the amine monomer compound containing 2 or more than 2 amino groups or imino groups. After the water-soluble electrode binder is applied to the electrochemical energy storage device, the binding power of an electrode plate can be improved, the volume expansion of an electrode active material is inhibited, the safety performance of the electrochemical energy storage device can be improved, and meanwhile, the cycle performance of the electrochemical energy storage device can be improved. The water-soluble electrode binder disclosed by the application is pollution-free and does not cause harm to human bodies and the environment. The preparation method of the electrode slice is simple and easy to implement, and the obtained electrode slice is safe and reliable.
Description
Technical field
This application involves energy storage device field more particularly to a kind of water-soluble binders for electrodes, electrode slice and its preparation side
Method and electrochemical energy storage device.
Background technique
Lithium ion battery is as one of most potential energy storage equipment, because of its high-energy density, high circulation service life, ring
The advantages that border friendly, is widely used in the fields such as portable mobile apparatus, electronic new-energy automobile and energy storage station.Lithium ion
Security performance and electrochemistry of the volume expansion that the negative electrode active material of battery generates in charge and discharge process to lithium ion battery
Performance has a significant impact, especially for the silicon-based anode active material with high-energy density, in charge and discharge process
Volume expansion can reach 300%, this, which also becomes, inhibits it in lithium ion battery one of an important factor for large-scale use, and selects
Selecting suitable binder is effective one of means for inhibiting negative electrode active material volume expansion.Suitable binder is because of its macromolecule
The powerful cohesive force of structure can effectively fix negative electrode active material, inhibit its volume expansion.In addition, binder is to lithium ion
The cycle performance of battery has a significant impact, if its own performance is bad, may be generated in lithium ion battery cyclic process dusting,
Phenomena such as demoulding.
Currently, the most common binder of lithium ion battery mainly has Kynoar (PVDF), sodium carboxymethylcellulose
(CMC), butadiene-styrene rubber (SBR) etc..PVDF binder is the more mature binder that most of positive electrode uses, and is had preferable
Caking property, but during producing pole piece PVDF binder need it is organic using a large amount of N-Methyl pyrrolidone (NMP)
Solvent is dissolved, and the volatility of NMP is stronger, and environmental pollution is big, and PVDF may be swollen in common electrolyte, from
And the stability of pole piece can be reduced.CMC and SBR is common water-based binder, but both binders are seldom used alone,
Because its viscosity is poor, and the mode of point sticky will lead to that pole piece mechanical property is poor, and especially SBR material is in high speed dispersion process
In may be interrupted macromolecular chain, production process is had some impact on.Therefore, prepare a kind of cohesive force is strong, mechanical property is good,
Easy processing and effectively pole piece can be inhibited to expand, especially inhibition graphite cathode active material, silicon-based anode active material or silicon-carbon
The volume expansion of alloy anode active material is market urgent need.
Summary of the invention
In view of the problems in the background art, the application is designed to provide a kind of water-soluble binders for electrodes, electricity
Pole piece and preparation method thereof and electrochemical energy storage device, the water solubility binders for electrodes has three-dimensional net structure, and has
There is good caking property, the cohesive force of electrode slice can be improved and inhibit the volume expansion of electrode active material, and then can improve
The security performance of electrochemical energy storage device, while the cycle performance of electrochemical energy storage device can also be improved.
In order to achieve the above object, the application's in a first aspect, this application provides a kind of water-soluble binders for electrodes,
It is prepared by water-soluble polymer and crosslinking agent.The water-soluble polymer contains-COOH functional group.The crosslinking agent
For the amine monomers compound containing 2 or 2 or more amidos or imido grpup and by containing 2 or 2 or more amidos or Asias
One or more of the amine polymer that the homopolymerization of amine monomers compound or copolymerization of amido are formed.
In the second aspect of the application, this application provides a kind of electrode slices comprising collector and diaphragm.The film
Piece is arranged on a current collector and including electrode active material and binders for electrodes.The binders for electrodes includes the application first
Water-soluble binders for electrodes described in aspect.
In the third aspect of the application, this application provides a kind of preparation method of electrode slice, it is used to prepare the present invention the
Electrode slice described in two aspects comprising step：By containing the water-soluble polymer of-COOH functional group, electrode active material, can
The conductive agent of choosing is uniformly mixed with deionized water is prepared into suspension；Backward suspension in crosslinking agent is added, being sufficiently stirred makes
Water-soluble polymer is reacted with crosslinking agent, obtains electrode slurry；Electrode slurry is coated in the surface of collector, dry,
Electrode slice is obtained after cold pressing.
In the fourth aspect of the application, this application provides a kind of electrochemical energy storage devices comprising the application second party
Electrode slice described in face.
Compared with the existing technology, the beneficial effect of the application includes：
The water-soluble binders for electrodes of the application has three-dimensional net structure, and has good caking property, when its application
After in electrochemical energy storage device, the cohesive force of electrode slice can be improved and inhibit the volume expansion of electrode active material, in turn
The security performance of electrochemical energy storage device can be improved, while the cycle performance of electrochemical energy storage device can also be improved.
The water-soluble binders for electrodes of the application can be prepared at room temperature, not need specially treated, while water solubility electricity
Pole binder is pollution-free, will not cause damages to human body and environment.
Preparation method is simple for the electrode slice of the application, and obtained electrode slice is safe and reliable.
Detailed description of the invention
Fig. 1 is the infrared test map of the water-soluble binders for electrodes of embodiment 2；
Fig. 2 is the cycle performance curve of embodiment 1 and comparative example 1.
Specific embodiment
It is stored up the following detailed description of according to the water-soluble binders for electrodes of the application, electrode slice and preparation method thereof and electrochemistry
It can device.
Illustrate the water-soluble binders for electrodes according to the application first aspect first.
The water-soluble binders for electrodes according to the application first aspect is prepared by water-soluble polymer and crosslinking agent
It forms.The water-soluble polymer contains-COOH functional group.The crosslinking agent is to contain 2 or 2 or more amidos or imido grpups
Amine monomers compound and by the homopolymerization of amine monomers compound or copolymerization containing 2 or 2 or more amidos or imido grpup
One or more of amine polymer of formation.
In the water-soluble binders for electrodes according to the application first aspect, contain on Water-soluble Polymer Molecules chain
Active function groups-COOH, containing 2 or 2 or more amidos or imido grpup in crosslinking agent, when water-soluble polymer and crosslinking agent
When reaction, the strand of water-soluble polymer can be crosslinked and be built bridge by amido in crosslinking agent or imido grpup, i.e., water-soluble
Property polymer molecular chain on-COOH and crosslinking agent in amido or imido grpup occur acylation reaction, formed have three-dimensional network
The water-soluble binders for electrodes of structure, wherein in crosslinking agent the number of amido or imido grpup at 2 or 2 or more, can for-
Acylation reaction occurs between COOH and amido or imido grpup, more reaction sites are provided, spatially to form three-dimensional network knot
The water-soluble binders for electrodes of structure provides guarantee.Water-soluble binders for electrodes with three-dimensional net structure has good viscous
Knot property, can increase the cohesive force in electrode slice between diaphragm and collector, so as to improve the safety of electrochemical energy storage device
Can, while there is the water-soluble binders for electrodes of three-dimensional net structure can be very good for electrode active material to be fixed on its three-dimensional
In network structure, prevents electrode active material from falling off from collector in electrochemical energy storage device charge and discharge process, prevent electricity
There is " picking " phenomenon over numerous cycles in pole piece.The strand of the water-soluble binders for electrodes of three-dimensional net structure is in crosslinking agent
Under the action of mutually involve, inhibit volume expansion of the electrode active material in charge and discharge process to a certain extent, at the same by
It is mutually involved in the strand of water-soluble binders for electrodes, when ion is deviate from from electrode active material, electrode active material
When volume expansion is restored, the strand of water-soluble binders for electrodes can also be restored to a certain extent, so as to
The volume expansion for further suppressing electrode active material improves the cycle performance of electrochemical energy storage device.
In the water-soluble binders for electrodes according to the application first aspect, the crosslinking agent and the water-soluble poly
The weight ratio for closing object is 0.01~0.20, if the weight ratio of crosslinking agent and water-soluble polymer is excessive, i.e., water-soluble electrode adhesion
The content of crosslinking agent is excessive in agent, then the crosslinking degree of water-soluble binders for electrodes is higher, molecular weight is larger, on the one hand will affect
On the other hand its dissolubility in deionized water will cause the decline of its caking property, influence the production and processing performance of electrode slice.
In the water-soluble binders for electrodes according to the application first aspect, the water-soluble polymer is selected from carboxylic acid
Quasi polymer and the monomer containing-COOH functional group and the block containing the formation of the monomer of amide groups and/or carboxylate are total
One or more of polymers.Preferably, the water-soluble polymer is selected from polyacrylic acid, polymethylacrylic acid, polyacrylic acid-
Polyacrylamide block copolymer, polymethylacrylic acid-polyacrylamide block copolymer, polymethylacrylic acid-polyacrylic acid
One or more of ester block copolymer, poly acrylic acid-poly acrylate based block copolymer.The optional autohemagglutination of polyacrylate
Methyl acrylate, polyethyl acrylate, butyl polyacrylate, polymethyl methacrylate, polyethyl methacrylate or poly- first
Base butyl acrylate.
In the water-soluble binders for electrodes according to the application first aspect, the crosslinking agent is selected from ethylenediamine, third
Diamines, phenylenediamine, diethylenetriamine, carbodiimides, tetramethyl dipropylenetriamine, polyethyene diamine, polyphenyl diamines, poly- carbonization two
One or more of poly- diethylenetriamine block copolymer of imines, polyethyene diamine-phenylenediamine block copolymer, polyethyene diamine-.
Secondly illustrate the electrode slice according to the application second aspect.
It include collector and diaphragm according to electrode slice described in the application second aspect.The diaphragm is arranged in collector
Above and including electrode active material and binders for electrodes.The binders for electrodes includes water-soluble described in the application first aspect
Property binders for electrodes.
In the electrode slice according to the application second aspect, the type of the collector is not limited specifically, institute
Stating water-soluble binders for electrodes both and can be used for anode can be used for cathode.Specifically, the collector is selected from aluminium foil, copper
One or more of foil, nickel foil, titanium foil, silver foil, monel foil, aluminium zircaloy foil, stainless steel foil.
Illustrate the preparation method of the electrode slice according to the application third aspect again.
According to the preparation method of electrode slice described in the application third aspect, it is used to prepare described in the application second aspect
Electrode slice, including step：By the water-soluble polymer containing-COOH functional group, electrode active material, optional conductive agent and go
Ionized water is uniformly mixed and is prepared into suspension；Backward suspension in crosslinking agent is added, be sufficiently stirred make water-soluble polymer with
Crosslinking agent is reacted, and electrode slurry is obtained；Electrode slurry is coated in the surface of collector, obtains electricity after drying, cold pressing
Pole piece.
In the preparation method of the electrode slice according to the application third aspect, using water-soluble polymer elder generation and electrode
Active material mixing, then adds the method that crosslinking agent is crosslinked, can in water-soluble polymer and cross-linking agents and
When bridging reaction occurs, electrode active material is preferably fixed on to the three-dimensional net structure for the water-soluble binders for electrodes to be formed
In, alleviate " picking " phenomenon that electrode slice occurs over numerous cycles, and when electrode active material occurs in charge and discharge process
When volume expansion, three-dimensional net structure can play buffer function, inhibit electrode active material in charge and discharge to a certain extent
Volume expansion in journey, simultaneously because the strand of water-soluble binders for electrodes mutually involves, when ion is from electrode active material
Middle abjection, when the volume expansion of electrode active material is restored, the strand of water-soluble binders for electrodes can also be certain
It is restored in degree, so as to further suppress the volume expansion of electrode active material.
In the preparation method of the electrode slice according to the application third aspect, when preparing suspension, will first contain-
The water-soluble polymer of COOH functional group is dissolved in deionized water and stirs evenly, and obtains water-soluble polymer aqueous solution, then
Electrode active material is added, optional conductive agent is uniformly mixed and is prepared into suspension.It is water-soluble in water-soluble polymer aqueous solution
Property polymer solid content be less than or equal to 50wt%, when the solid content of water-soluble polymer is excessively high, on the one hand, water-soluble polymer
The viscosity of aqueous solution is larger or even part aqueous polymer possibly can not be completely dissolved in water, nothing after crosslinking agent is added
Method is sufficiently reacted, and the solid content of another aspect water-soluble polymer is excessively high, is unable to fully mix when mixing with electrode active material,
The homogeneity of electrode slurry is influenced, and then influences the processing performance and chemical property of electrode slice.
Finally illustrate the electrochemical energy storage device according to the application fourth aspect.
It include the electricity according to the application second aspect according to electrochemical energy storage device described in the application fourth aspect
Pole piece.
In the electrochemical energy storage device according to the application fourth aspect, the electrochemical energy storage device includes anode
Piece, negative electrode tab, isolation film, pack case and electrolyte etc..Both it can be used for according to electrode slice described in the application third aspect
The anode of electrochemical energy storage device can be used for cathode.In embodiments herein, the application third aspect institute is only shown
Embodiment of the electrode slice stated for the cathode of electrochemical energy storage device, but the application is without being limited thereto.
In the electrochemical energy storage device according to the application fourth aspect, it should be noted that the electrochemistry storage
Energy device can be lithium ion battery, lithium metal battery or supercapacitor.In embodiments herein, energy storage device is only shown
For the embodiment of lithium ion battery, but the application is without being limited thereto.
In lithium ion battery, positive electrode active materials are selected from the material that can deviate from, receive lithium ion, specifically, described
Positive electrode active materials are selected from lithium transition-metal oxide, include lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, lithium nickel manganese
Oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide and above-mentioned lithium transition-metal oxide add other transition metal
Or nontransition metal or nonmetallic obtained one or more of compound.Positive conductive agent be selected from acetylene black, conductive black,
One or more of carbon fiber (VGCF), carbon nanotube (CNT), Ketjen black.
In lithium ion battery, negative electrode active material is selected from the material that can receive, deviate from lithium ion, specifically, described
Negative electrode active material can be selected from one in artificial graphite, natural graphite, silicon, silicon oxide compound, silicon-base alloy and kamash alloy
Kind is several.Cathode conductive agent is selected from acetylene black, active carbon, conductive black, carbon fiber (VGCF), carbon nanotube (CNT), section's qin
It is one or more of black.
In lithium ion battery, the electrolyte can be liquid electrolyte, and the electrolyte may include lithium salts and organic
Solvent.
In lithium ion battery, the specific type of the lithium salts is unrestricted.Specifically, the lithium salts can be selected from LiPF6、
LiBF4、LiN(SO2F)2(being abbreviated as LiFSI), LiN (CF3SO2)2(being abbreviated as LiTFSI), LiClO4、LiAsF6、LiB(C2O4)2
(being abbreviated as LiBOB), LiBF2C2O4One or more of (being abbreviated as LiDFOB).
In lithium ion battery, the specific type of the organic solvent is not particularly limited, can be according to actual needs
It is selected.Preferably, using non-aqueous organic solvent.The non-aqueous organic solvent may include the carbonic ester of any kind, carboxylic acid
Ester.Carbonic ester may include cyclic carbonate or linear carbonate.The non-aqueous organic solvent may also include the halogenated of carbonic ester
Compound.Specifically, the organic solvent is selected from ethylene carbonate (EC), propene carbonate (PC), butylene carbonate, carbonic acid Asia
Pentyl ester, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate (DEC), dipropyl carbonate, methyl ethyl carbonate, γ-Ding Nei
One or more of ester, methyl formate, Ethyl formate, ethyl propionate, propyl propionate, tetrahydrofuran.
In lithium ion battery, the type of the isolation film is not specifically limited, and can be selected according to actual needs.
Below with reference to embodiment, the application is further described.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.The case where electrochemical energy storage device is lithium ion battery is only shown in embodiment, but is applied
It is without being limited thereto.In the following embodiments, reagent, material and the instrument used such as not special explanation, it is commercially available
It obtains.
Embodiment 1
(1) preparation of negative electrode tab
Water-soluble polymer polyacrylic acid (PAA) is dissolved in deionized water first and is uniformly mixing to obtain PAA aqueous solution,
In, the solid content of PAA aqueous solution is 25%；Then by PAA aqueous solution, negative electrode active material, cathode conductive agent active carbon according to
Weight ratio is 10:88:2 are sufficiently mixed, and continue plus deionized water stirs evenly, obtain suspension, wherein the solid content of suspension
It is 40%, negative electrode active material is 30% mixture for aoxidizing sub- silicon and 70% graphite；Then crosslinking agent is added into suspension
Ethylenediamine continues to stir, and crosslinks PAA with ethylenediamine and reacts and be uniformly mixed with negative electrode active material, after stirring
Obtain negative electrode slurry, wherein the weight ratio of crosslinking agent ethylenediamine and water-soluble polymer PAA are 1:50, agitation revolution is
1500rad/min；Negative electrode slurry is finally coated in the two sides of the negative current collector copper foil of 12 μ m-thicks, is dried at 80 DEG C again later
It is dry, then pass through cold pressing, slitting, soldering polar ear, negative electrode tab is made.
(2) preparation of positive plate
By positive electrode active materials cobalt acid lithium (LiCoO2), binder Kynoar (PVDF), conductive agent acetylene black according to
Weight ratio is 97:2:1 is mixed, and is added N-Methyl pyrrolidone (NMP), is stirred evenly, is obtained under de-airing mixer effect
Obtain anode sizing agent；Anode sizing agent is evenly applied on the plus plate current-collecting body aluminium foil with a thickness of 12 μm；Aluminium foil is dried in room temperature
After be transferred to 120 DEG C of oven drying 1h, then pass through cold pressing, slitting, soldering polar ear, obtained positive plate.
(3) preparation of electrolyte
In water content<In the argon atmosphere glove box of 10ppm, by ethylene carbonate (EC), propene carbonate (PC), carbonic acid
Dimethyl ester (DEC) is EC according to volume ratio:PC:DEC=1:1:1 is mixed, then by sufficiently dry lithium salts LiPF6Dissolution
In mixed organic solvents, electrolyte is obtained after mixing, wherein LiPF6Concentration be 1M.
(4) preparation of isolation film
Using polypropylene film as isolation film.
(5) preparation of lithium ion battery
Positive plate obtained, isolation film, negative electrode tab are folded in order, are in isolation film among positive/negative plate, is wound
Obtain naked battery core；Naked battery core is placed in battery packages shell, injects electrolyte later, using processes such as chemical conversion, standings, is completed
The preparation of lithium ion battery.
Embodiment 2
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of negative electrode tab
The weight ratio of crosslinking agent ethylenediamine and water-soluble polymer PAA are 1:25.
Embodiment 3
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of negative electrode tab
Water-soluble polymer is polymethylacrylic acid-polyacrylamide block copolymer；
Negative electrode active material is graphite.
Embodiment 4
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of negative electrode tab
Negative electrode active material is graphite；
The weight ratio of crosslinking agent ethylenediamine and water-soluble polymer PAA are 1:25.
Embodiment 5
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of negative electrode tab
Negative electrode active material is 10% mixture for aoxidizing sub- silicon and 90% graphite；
Crosslinking agent is diethylenetriamine；
The weight ratio of crosslinking agent diethylenetriamine and water-soluble polymer PAA are 5:95.
Embodiment 6
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of negative electrode tab
Water-soluble polymer is poly acrylic acid-poly methyl acrylate block copolymer；
Negative electrode active material is 20% mixture for aoxidizing sub- silicon and 80% graphite；
Crosslinking agent is phenylenediamine；
The weight ratio of crosslinking agent phenylenediamine and water-soluble polymer PAA are 10:90.
Embodiment 7
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of negative electrode tab
Crosslinking agent is polycarbodiimide；
The weight ratio of crosslinking agent polycarbodiimide and water-soluble polymer PAA are 15:85.
Comparative example 1
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of negative electrode tab
Water-soluble polymer polyacrylic acid (PAA) is dissolved in deionized water first and is uniformly mixing to obtain PAA aqueous solution,
In, the solid content of PAA aqueous solution is 25%；Then by PAA aqueous solution, negative electrode active material, cathode conductive agent active carbon according to
Weight ratio is 10:88:2 are sufficiently mixed, and continue plus deionized water stirs evenly, obtain negative electrode slurry, wherein negative electrode slurry is consolidated
Content is 40%, and negative electrode active material is 30% mixture for aoxidizing sub- silicon and 70% graphite；Then negative electrode slurry is coated in
The two sides of the negative current collector copper foil of 12 μ m-thicks, is dried at 80 DEG C again later, then passes through cold pressing, slitting, soldering polar ear, system
Obtain negative electrode tab.
Comparative example 2
With comparative example 1, difference is the preparation process of lithium ion battery,
(1) preparation of negative electrode tab
Negative electrode active material is graphite.
Comparative example 3
With comparative example 1, difference is the preparation process of lithium ion battery,
(1) preparation of negative electrode tab
Negative electrode active material is 10% mixture for aoxidizing sub- silicon and 90% graphite.
Comparative example 4
With comparative example 1, difference is the preparation process of lithium ion battery,
(1) preparation of negative electrode tab
Negative electrode active material is 20% mixture for aoxidizing sub- silicon and 80% graphite.
Comparative example 5
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of negative electrode tab
Water-soluble polymer polyacrylic acid (PAA) is dissolved in deionized water first and is uniformly mixing to obtain PAA aqueous solution,
In, the solid content of PAA aqueous solution is 25%；Then crosslinking agent ethylenediamine is added in PAA aqueous solution, stirring makes PAA and second two
Amine crosslinks reaction, obtains water-soluble electrode adhesion agent solution, wherein crosslinking agent ethylenediamine is with water-soluble polymer PAA's
Weight ratio is 1:50, agitation revolution 1500rad/min；Then by water-soluble binders for electrodes aqueous solution, negative electrode active material,
Cathode conductive agent active carbon is 10 according to weight ratio:88:2 are sufficiently mixed, and deionized water is added to stir evenly, and obtain negative electrode slurry,
Wherein the solid content of negative electrode slurry is 40%, and negative electrode active material is 30% mixture for aoxidizing sub- silicon and 70% graphite；Finally
By negative electrode slurry be coated in 12 μ m-thicks negative current collector copper foil two sides, dried at 80 DEG C again later, then by cold pressing,
Negative electrode tab is made in slitting, soldering polar ear.
The parameter of table 1 embodiment 1-7 and comparative example 1-5
The test process of lithium ion battery will be illustrated next.
(1) the cycle performance test of lithium ion battery
It with 0.7C constant-current charge to voltage is 4.4V by lithium ion battery, extremely with 4.4V constant-voltage charge later at 25 DEG C
Electric current is 0.05C, and lithium ion battery reaches fully charged state at this time, stands 5min later, is with 0.5C constant-current discharge to voltage
3.0V, then 5min is stood, this is a cycle charge discharge electric process, records the discharge capacity of lithium ion battery the 1st time circulation, then
Circulation is charged and discharged, and records the discharge capacity after lithium ion battery the 100th time circulation.Every group takes 4 lithium-ion electrics
Pond carries out cycle performance test.
Capacity retention ratio (%)=lithium ion battery the 100th time electric discharge recycled after lithium ion battery recycles 100 times is held
Discharge capacity × 100% of amount/lithium ion battery the 1st time circulation.
(2) the cohesive force test of negative electrode tab
Using 180 ° of peel strength test methods of industry universal, the cohesive force of negative electrode tab is tested.Test process is as follows：It takes
Negative electrode tab to be measured, with blade interception width be 0.02m, the sample that length is 0.1m；Special two-side adhesive tape, which is affixed on width, is
On 0.02m, the steel plate that length is 0.2m, the width of double faced adhesive tape is 0.02m, length 0.09m, wherein the one of double faced adhesive tape
It holds concordant with one end of steel plate；The negative electrode tab sample of interception is attached on double-sided adhesive, test is face-down；It is 0.02m, length by width
The paper tape that degree is 0.15m is inserted into below negative electrode tab, and is fixed with wrinkle glue；Steel plate is not pasted to one end puller system of negative electrode tab
Lower fixture fix, paper tape is flipped up, is fixed with upper fixture, opens puller system, the speed that puller system is run up is
0.05m/min；Pulling force F shown when puller system when record negative electrode tab is removed from double-sided adhesive, every group takes 4 negative electrode tab samples
It is tested and is averaged.
The cohesive force (N/m) of negative electrode tab=pulling force F/ negative electrode tab sample width.
(3) the expansion test of cathode membrane
The original depth of cathode membrane is measured first, and is denoted as H0, will recycle by the above-mentioned charging and discharging of n times and completely fill
Lithium ion battery dismantling afterwards, the thickness of obtained cathode membrane are denoted as HN。
Lithium ion battery recycles thickness swelling=(H of cathode membrane after n timesN/H0- 1) × 100%.
The performance test results of table 2 embodiment 1-7 and comparative example 1-5
As can be seen from Table 1 and Table 2, using the water-soluble binders for electrodes of the application to the normal temperature circulation of lithium ion battery
The thickness swelling of performance, the cohesive force of negative electrode tab and cathode membrane has clear improvement, although the type difference of crosslinking agent,
Content is different, negative electrode active material type is different, variant to the performance improvement of lithium ion battery, but overall improvement is excellent
In the lithium ion battery for making binder only with water-soluble polymer.
In embodiment 1-7 and comparative example 1-4, after crosslinking agent reaction is added in water-soluble polymer, lithium ion battery
Normal-temperature circulating performance improved, and the thickness swelling of cathode membrane is also inhibited.In conjunction with Fig. 2, polypropylene is used only
Capacity retention ratio after the lithium ion battery (comparative example 1) that acid makees binder recycles 100 times is 90.1%, and uses the application's
Capacity retention ratio after the lithium ion battery (embodiment 1) of water-soluble binders for electrodes recycles 100 times is up to 98.1%, lithium ion
The normal-temperature circulating performance of battery is improved significantly.It can be seen that crosslinking agent ethylenediamine in conjunction with Fig. 1 infrared test result and add
Acylation reaction has occurred in (embodiment 2) amido and carboxylic acid group after entering into water-soluble polymer polyacrylic acid, occurs in Fig. 1
- NH- bending vibration characteristic peak (the 1557cm of amide groups-1) and amide groups carbonyl C=O stretching vibration characteristic peak (1644cm-1), crosslinking agent forms crosslinking and bridge formation process between Water-soluble Polymer Molecules chain, obtains the water with three-dimensional net structure
On the one hand insoluble electrode binder improves the cohesive force of negative electrode tab, on the other hand the binder energy of this three-dimensional net structure
Negative electrode active material is preferably fixed, so as to improve " picking " phenomenon that negative electrode tab occurs over numerous cycles, certain journey
The normal-temperature circulating performance of lithium ion battery is improved on degree.
In embodiment 1-7 and comparative example 1-4, water-soluble binders for electrodes is in terms of the thickness swelling for inhibiting cathode membrane
Also there is different degrees of improvement.In initial cycle, it is slightly smaller to the inhibitory effect of the thickness swelling of cathode membrane, but passes through
It crosses after repeatedly circulation, the effect inhibited significantly increases.This is because in comparative example 1-4, the water-soluble polymer of use
Binder polyacrylic acid is chain structure, and over numerous cycles, the volume of negative electrode active material expands, and chain structure is gathered
Acrylic acid is difficult to return to original state, and after crosslinking agent is added, crosslinking agent forms crosslinking between the chain and chain of polyacrylic acid
And bridge formation, the water-soluble binders for electrodes of three-dimensional net structure is obtained, is mutually involved between polyacrylic acid strand, in lithium ion
After negative electrode active material abjection, polyacrylic acid strand can be made to restore to a certain extent, to inhibit cathode membrane
Thickness swelling.Embodiment 7 carries out cross-linking reaction using the crosslinking agent and polyacrylic acid of polymer architecture, in polymeric crosslinker
Crosslinking is formed between strand and the strand of polyacrylic acid and is built bridge, it can to the inhibitory effect of the thickness swelling of cathode membrane
It can be more preferable.
In embodiment 1 and comparative example 5, it is uniformly mixed in water-soluble polymer with negative electrode active material using by crosslinking agent
The method added afterwards can make negative electrode active material more uniformly be dispersed in the water-soluble binders for electrodes being cross-linked to form
In three-dimensional net structure, negative electrode active material can be preferably fixed, and inhibit the volume expansion of negative electrode active material, inhibit negative
The thickness swelling of pole diaphragm.And be first cross-linked to form in comparative example 5 water-soluble binders for electrodes will lead to negative electrode active material can not
It is dispersed in the three-dimensional net structure of water-soluble binders for electrodes, the inhibition to negative electrode active material volume expansion is caused to be imitated
Fruit is poorer than the former, therefore poor to the inhibitory effect of the thickness swelling of cathode membrane, to the cycle performance of lithium ion battery
Improvement is also unobvious.
According to the disclosure and teachings of the above specification, the application those skilled in the art can also be to above-mentioned embodiment party
Formula carries out change and modification appropriate.Therefore, the application is not limited to specific embodiment disclosed and described above, to this
Some modifications and changes of application should also be as falling into the protection scope of claims hereof.In addition, although this specification
In use some specific terms, these terms are merely for convenience of description, not to the application constitute any restrictions.
Claims (10)
1. a kind of water solubility binders for electrodes, which is characterized in that be prepared by water-soluble polymer and crosslinking agent；
The water-soluble polymer contains-COOH functional group；
The crosslinking agent is for the amine monomers compound containing 2 or 2 or more amidos or imido grpup and by containing 2 or 2
One or more of the amine polymer that the homopolymerization of amine monomers compound or copolymerization of a above amido or imido grpup are formed.
2. water solubility binders for electrodes according to claim 1, which is characterized in that the crosslinking agent and the water-soluble poly
The weight ratio for closing object is 0.01~0.20.
3. water solubility binders for electrodes according to claim 1, which is characterized in that the water-soluble polymer is selected from carboxylic acid
Quasi polymer and the monomer containing-COOH functional group and the block containing the formation of the monomer of amide groups and/or carboxylate are total
One or more of polymers.
4. water solubility binders for electrodes according to claim 3, which is characterized in that the water-soluble polymer is selected from poly- third
Olefin(e) acid, polymethylacrylic acid, poly acrylic acid-poly acrylamide block copolymer, polymethylacrylic acid-polyacrylamide block are total
One of polymers, polymethylacrylic acid-polyacrylic acid ester block copolymer, poly acrylic acid-poly acrylate block copolymer
Or it is several.
5. water solubility binders for electrodes according to claim 1, which is characterized in that the crosslinking agent is selected from ethylenediamine, third
Diamines, phenylenediamine, diethylenetriamine, carbodiimides, tetramethyl dipropylenetriamine, polyethyene diamine, polyphenyl diamines, poly- carbonization two
One of imines, polyethyene diamine-polyphenyl diamines block copolymer, the poly- diethylenetriamine block copolymer of polyethyene diamine-are several
Kind.
6. a kind of electrode slice, including：
Collector；And
Diaphragm is arranged on a current collector and including electrode active material and binders for electrodes；
It is characterized in that, the binders for electrodes includes water-soluble electrode adhesion according to any one of claims 1-5
Agent.
7. a kind of preparation method of electrode slice, is used to prepare electrode slice as claimed in claim 6, which is characterized in that including step：
Water-soluble polymer containing-COOH functional group, electrode active material, optional conductive agent are mixed with deionized water
It is even to be prepared into suspension；
Backward suspension in crosslinking agent is added, being sufficiently stirred reacts water-soluble polymer with crosslinking agent, obtains electrode
Slurry；
Electrode slurry is coated in the surface of collector, obtains electrode slice after drying, cold pressing.
8. the preparation method of electrode slice according to claim 7, which is characterized in that when preparing suspension, will first contain-
The water-soluble polymer of COOH functional group is dissolved in deionized water and stirs evenly, and obtains water-soluble polymer aqueous solution, then
Electrode active material is added, optional conductive agent is uniformly mixed and is prepared into suspension.
9. the preparation method of electrode slice according to claim 8, which is characterized in that in water-soluble polymer aqueous solution,
The solid content of water-soluble polymer is less than or equal to 50wt%.
10. a kind of electrochemical energy storage device, which is characterized in that including electrode slice according to claim 6.
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| CN109786747A (en) * | 2018-12-29 | 2019-05-21 | 南方科技大学 | Lithium ion battery binder and its preparation method and application |
| CN110350195A (en) * | 2019-06-24 | 2019-10-18 | 北京科技大学 | A kind of preparation method of negative electrode of lithium ion battery binder and negative electrode of lithium ion battery |
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