CN116759576B - Lithium battery electrode coating slurry containing modified polyacrylic acid binder, and preparation method and application thereof - Google Patents
Lithium battery electrode coating slurry containing modified polyacrylic acid binder, and preparation method and application thereof Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 48
- 229920002125 Sokalan® Polymers 0.000 title claims abstract description 46
- 239000004584 polyacrylic acid Substances 0.000 title claims abstract description 46
- 239000011230 binding agent Substances 0.000 title claims abstract description 31
- 239000006255 coating slurry Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 47
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 21
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 14
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000006258 conductive agent Substances 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000013067 intermediate product Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000010526 radical polymerization reaction Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 14
- 238000009830 intercalation Methods 0.000 abstract description 5
- 230000002687 intercalation Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 4
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention particularly relates to a lithium battery electrode coating slurry containing a modified polyacrylic acid binder, a preparation method and application thereof, wherein the lithium battery electrode coating slurry containing the modified polyacrylic acid binder mainly comprises the following components: 10-15 parts of modified nano-silicon, 10-15 parts of nano-silicon, 5-10 parts of conductive agent and 10-15 parts of modified polyacrylic acid, wherein the raw materials of the modified polyacrylic acid are acrylic acid and pentaerythritol, and the raw materials of the modified nano-silicon are nano-silicon with hydroxylated surface and dodecyl carboxylic acid. The lithium battery silicon electrode film prepared by the electrode coating slurry has excellent mechanical property and strong bonding capability, can effectively tie up crushed silicon in the cycle process of a nano silicon electrode, has excellent stretchability, and can effectively accommodate huge volume expansion of silicon in the lithium intercalation process.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a lithium battery electrode coating slurry containing a modified polyacrylic acid binder, and a preparation method and application thereof.
Background
The lithium battery is widely applied to the fields of electric automobiles, smart phones, notebook computers and the like as a battery with high performance, high efficiency, light weight and environmental protection. In a lithium ion battery, silicon is used as a novel electrode material, and has high specific capacity and rate capability, but in the charge and discharge process, silicon can undergo an intercalation and deintercalation lithium reaction, so that the electrode material undergoes great volume change. When the silicon electrode is embedded with lithium ions, silicon can form lithium silicon alloy, and the volume can be obviously expanded; when the silicon electrode releases lithium ions, the lithium silicon alloy is gradually decomposed, and the volume is obviously shrunk. Such volume changes may cause cracking and flaking of the electrode material, thereby affecting the performance and safety of the battery. Although silicon electrodes have great volume changes in the process of inserting and extracting lithium, their high specific capacity and rate capability make them one of the important development directions of next-generation high-performance lithium ion batteries, so researchers are continually exploring various solutions to improve the stability and cycle life of silicon electrodes.
Research shows that the polymer binder plays a very key role in maintaining the integrity of the anode structure and improving the cycle performance of the lithium battery, and the binder can greatly improve the cycle stability of the silicon anode. However, conventional polyvinylidene fluoride binders are not suitable for silicon cathodes and cannot accommodate the large volume changes in the intercalation and deintercalation lithium reactions due to the weak van der waals interactions between polyvinylidene fluoride and the silicon material and copper current collector.
CN105047935a discloses a composite binder, a preparation method thereof and a lithium battery, and the composite binder can effectively improve the structural firmness of an electrode in the charge and discharge process and the cycle stability of the lithium battery, and can effectively improve the rate capability and capacity of the lithium battery. However, when the resin prepared by the method is used for a lithium battery binder, the tensile property is poor, and the resin cannot adapt to the huge volume change in the lithium intercalation and deintercalation reaction.
CN104530276a discloses a preparation method of PVDF resin special for lithium battery binder, the resin synthesized by the method comprises emulsifying agent, vinylidene fluoride monomer, initiator and molecular weight regulator, the preparation method has simple process, low risk and high selectivity. However, when the resin prepared by the method is used for a lithium battery binder, the problems of large consumption of PVDF resin, poor binding capacity, poor tensile property and the like exist
Therefore, there is a need to develop a lithium battery electrode coating paste by reasonable design of the binder to solve these problems faced by the silicon electrode.
Disclosure of Invention
In order to solve the problems, the invention provides a lithium battery electrode coating slurry containing a modified polyacrylic acid binder.
The invention aims to provide a lithium battery electrode coating slurry containing a modified polyacrylic acid binder, which comprises the following components in parts by weight:
wherein the raw materials of the modified polyacrylic acid are acrylic acid and pentaerythritol.
Further, the conductive agent is selected from carbon black, conductive graphite or carbon fiber.
Further, the particle size of the nano silicon is 100-500nm.
Further, the raw materials of the modified nano-silicon are nano-silicon with hydroxylated surface and dodecyl carboxylic acid.
Further, the water is selected from deionized water.
Another object of the present invention is to provide a method for preparing the above-mentioned modified polyacrylic acid binder-containing lithium battery electrode coating paste, comprising the steps of:
s1, carrying out esterification reaction on acrylic acid and pentaerythritol under the condition that concentrated sulfuric acid is used as a catalyst to obtain an intermediate product;
s2, carrying out free radical polymerization on the intermediate product and an acrylic acid monomer to obtain the modified polyacrylic acid;
s3, soaking the hydroxylated nano silicon in dodecyl carboxylic acid, heating by ultrasonic, and then washing to obtain the modified nano silicon;
s4, blending the modified polyacrylic acid, the modified nano silicon and other components to form slurry.
Further, in the step S1, the molar ratio of the acrylic acid to the pentaerythritol is 6:1-4:1.
Further, in step S2, the catalysts used in the radical polymerization are ammonium persulfate and sodium bisulfite.
Further, in step S2, the molar ratio of the intermediate product to the acrylic acid monomer is 1:30-50.
Further, in step S3, the hydroxylated nano silicon is prepared as follows: adding nano silicon into a mixed solution consisting of ammonia water, hydrogen peroxide and water, heating and stirring, washing with water, filtering and drying in vacuum to obtain hydroxylated nano silicon.
Another object of the present invention is to provide the use of the above-mentioned modified polyacrylic acid binder-containing lithium battery electrode coating paste: and uniformly coating the lithium battery electrode coating slurry containing the modified polyacrylic acid adhesive on the surface of a copper foil current collector, and drying in a vacuum environment to obtain the lithium battery silicon electrode slice containing the modified polyacrylic acid adhesive.
The invention has the following beneficial effects:
1. in the preparation process of the modified polyacrylic acid adhesive, carboxyl of acrylic acid can be subjected to esterification reaction with hydroxyl of pentaerythritol, and then double bonds are subjected to free radical polymerization, so that a compact three-dimensional reticular polymer structure is formed.
2. The modified polyacrylic acid adhesive slurry is prepared by grafting and polymerizing pentaerythritol and acrylic acid, and a large amount of oxygen-containing functional groups exist on the obtained modified polyacrylic acid and can form hydrogen bonds with hydroxyl groups remained on the surface of silicon, so that the modified polyacrylic acid and silicon particles have strong interaction, the coating slurry has stronger bonding capability, and the coating slurry can be firmly bonded with a silicon electrode plate of a lithium battery.
3. The modified nano silicon is obtained by the reaction of the hydroxylated nano silicon and the dodecyl carboxylic acid, in the modification process, hydroxyl groups contained on the surface of the nano silicon and carboxyl groups in the dodecyl carboxylic acid are subjected to esterification reaction to form the modified nano silicon, so that the dispersibility of the nano silicon in a polymer is improved, and the nano silicon powder has the characteristics of small particle size, large surface area, high surface activity and the like, and can effectively improve the binding force and compatibility of the nano silicon and other components of the lithium battery electrode coating slurry.
4. The lithium battery silicon electrode film prepared by using the electrode coating slurry has excellent mechanical properties, can effectively tie up crushed silicon in the cycle process of a nano silicon electrode, has excellent stretchability, and can effectively accommodate huge volume expansion of silicon in the lithium intercalation process.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments and protection of the present invention are not limited thereto. It should be noted that the following processes, if not specifically described in detail, can be realized or understood by those skilled in the art with reference to the prior art.
The nano silicon has the particle size of 100nm and is purchased from Beijing alfa Angstrom chemical Co., ltd;
the acrylic acid is purchased from Shandong Ying chemical industry Co., ltd;
the conductive agent is carbon black, and is purchased from Tianjin Yibo chemical industry Co., ltd;
the pentaerythritol disclosed by the invention is purchased from Sharpe Kazakhstan commercial limited company;
the parts referred to in the present invention refer to parts by weight unless specifically indicated otherwise.
Example 1
A lithium battery electrode coating paste containing a modified polyacrylic acid binder, comprising the following components:
preparation of hydroxylated nano silicon: and (3) soaking nano silicon in a mixed solution consisting of 25% ammonia water and 25% hydrogen peroxide (nano silicon: ammonia water: hydrogen peroxide=1:10:10, n/n/n), heating to boiling, stirring for 1h, washing with water, filtering, and vacuum drying for 2h to obtain the hydroxylated nano silicon.
The preparation of the lithium battery electrode coating slurry containing the modified polyacrylic acid binder is as follows:
s1, under the nitrogen atmosphere, adding acrylic acid and pentaerythritol (acrylic acid: pentaerythritol=6:1, n/n) into a reaction kettle, then adding concentrated sulfuric acid with 0.2wt% of acrylic acid as a catalyst, heating to 90 ℃ for reaction for 4 hours, and removing water under reduced pressure to obtain an intermediate product;
s2, adding the intermediate product into an acrylic acid monomer (the molar ratio of the intermediate product to the acrylic acid monomer is 1:30, n/n) under the nitrogen atmosphere, then adding ammonium persulfate and sodium bisulfate as an initiator (the ammonium persulfate is 0.05wt percent and the sodium bisulfate is 0.01wt percent), keeping the temperature at 90 ℃ for reaction for 6 hours, and filtering to remove impurities to obtain the modified polyacrylic acid;
s3, soaking the hydroxylated nano silicon in dodecyl carboxylic acid (dodecyl carboxylic acid: nano silicon=10:0.1, n/n), stirring at 90 ℃, simultaneously carrying out ultrasonic reaction for 4 hours, repeatedly washing with water, removing unreacted raw materials and byproducts, and drying to obtain modified nano silicon;
and S4, mixing 10 parts of modified nano-silicon, 10 parts of modified polyacrylic acid and 5 parts of conductive agent in 80 parts of deionized water, and uniformly stirring for 3 hours to obtain the lithium battery electrode coating slurry containing the modified polyacrylic acid adhesive.
Example 2
A lithium battery electrode coating paste containing a modified polyacrylic acid binder, comprising the following components:
preparation of hydroxylated nano silicon: the nano silicon is soaked in a mixed solution composed of 25% ammonia water and 25% hydrogen peroxide (nano silicon: ammonia water: hydrogen peroxide=1:10:10, n/n/n), heated to boiling and stirred for 1h, and then washed with water, filtered and dried in vacuum for 2h to obtain the hydroxylated nano silicon.
The preparation of the lithium battery electrode coating slurry containing the modified polyacrylic acid binder is as follows:
s1, under the nitrogen atmosphere, adding acrylic acid and pentaerythritol (acrylic acid: pentaerythritol=6:1, n/n) into a reaction kettle, then adding concentrated sulfuric acid with 0.2wt% of acrylic acid as a catalyst, heating to 90 ℃ for reaction for 4 hours, and removing water under reduced pressure to obtain an intermediate product;
s2, adding the intermediate product into an acrylic acid monomer (the molar ratio of the intermediate product to the acrylic acid monomer is 1:30, n/n) under the nitrogen atmosphere, then adding ammonium persulfate and sodium bisulfate as an initiator (the ammonium persulfate is 0.05wt percent and the sodium bisulfate is 0.01wt percent), keeping the temperature at 90 ℃ for reaction for 6 hours, and filtering to remove impurities to obtain the modified polyacrylic acid;
s3, soaking the hydroxylated nano silicon in dodecyl carboxylic acid (dodecyl carboxylic acid: nano silicon=10:0.1, n/n), stirring at 90 ℃, simultaneously carrying out ultrasonic reaction for 4 hours, repeatedly washing with water, removing unreacted raw materials and byproducts, and drying to obtain the modified nano silicon;
and S4, mixing 15 parts of modified nano-silicon, 15 parts of modified polyacrylic acid and 8 parts of conductive agent in 100 parts of deionized water, and uniformly stirring for 3 hours to obtain the lithium battery electrode coating slurry containing the modified polyacrylic acid adhesive.
Comparative example 1
In comparative example 1, the raw materials and the preparation method were the same as in example 1, except that the electrode coating paste in the step of comparative example 1 did not contain modified polyacrylic acid, but was replaced with polyacrylic acid of equal parts by mass.
Application example 1
The lithium battery electrode coating slurries prepared in example 1 and comparative example 1 were uniformly coated on a copper foil current collector, and then the copper foil was vacuum-dried at 120 ℃ for 12 hours to prepare a lithium battery silicon electrode sheet.
Test example 1
Mechanical property test: the electrode coating slurries obtained in example 1 and comparative example 1 were subjected to tensile property test by preparing 3 film samples (width of 1m, thickness of 15 μm) with reference to ASTM D638-14.
Peel force test: the electrode coating slurries obtained in example 1 and comparative example 1 were coated on copper foil to prepare 3 electrode sheets of 2cm×3cm, and a peeling test was performed at a speed of 200 μm/s, and the maximum value displayed by the test apparatus when the copper foil was completely peeled was peeling force.
The results obtained are shown in Table 1.
Table 1 various performance indexes of samples prepared using the electrode coating slurries of example 1 and comparative example 1
As can be seen from table 1, the samples of example 1 have better average tensile strength and average peel force than the samples of comparative example 1, which demonstrates that the lithium battery coating paste containing the modified polyacrylic acid binder of the present invention has strong binding ability and excellent tensile properties, and can adapt to pole piece pulverization caused by the volume deformation of silicon particles, thereby better maintaining the integrity of the electrode.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (8)
1. The lithium battery electrode coating slurry containing the modified polyacrylic acid binder is characterized by comprising the following components in parts by weight:
10-15 parts of modified nano silicon
10-15 parts of nano silicon
5-10 parts of conductive agent
10-15 parts of modified polyacrylic acid
80-100 parts of water;
wherein, the raw materials of the modified polyacrylic acid are acrylic acid and pentaerythritol, and the raw materials of the modified nano silicon are nano silicon with hydroxylated surface and dodecyl carboxylic acid;
the preparation method of the lithium battery electrode coating slurry containing the modified polyacrylic acid binder comprises the following steps:
s1, carrying out esterification reaction on acrylic acid and pentaerythritol under the condition that concentrated sulfuric acid is used as a catalyst to obtain an intermediate product;
s2, carrying out free radical polymerization on the intermediate product and an acrylic acid monomer to obtain the modified polyacrylic acid;
s3, soaking the nano silicon with the hydroxylated surface in dodecyl carboxylic acid, heating by ultrasonic, and then washing to obtain the modified nano silicon;
s4, blending the modified polyacrylic acid, the modified nano silicon and other components to form slurry.
2. The lithium battery electrode coating paste containing a modified polyacrylic acid binder according to claim 1, wherein the conductive agent is selected from carbon black, conductive graphite, or carbon fiber.
3. The lithium battery electrode coating paste containing a modified polyacrylic acid binder according to claim 1, wherein the nano silicon has a particle size of 100 to 500nm.
4. The lithium battery electrode coating paste containing a modified polyacrylic acid binder of claim 1, wherein the water is selected from deionized water.
5. The lithium battery electrode coating paste containing a modified polyacrylic acid binder according to claim 1, wherein in step S1, the molar ratio of acrylic acid to pentaerythritol is 6:1 to 4:1.
6. The lithium battery electrode coating paste containing the modified polyacrylic acid binder according to claim 1, wherein in step S2, the catalyst used for the radical polymerization is ammonium persulfate and sodium bisulfite.
7. The lithium battery electrode coating paste containing a modified polyacrylic acid binder according to claim 1, wherein in step S2, the molar ratio of the intermediate product to acrylic acid monomer is 1:30-50.
8. Use of a lithium battery electrode coating paste containing a modified polyacrylic acid binder according to any one of claims 1 to 7 in a silicon electrode.
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| CN202310665589.6A CN116759576B (en) | 2023-06-07 | 2023-06-07 | Lithium battery electrode coating slurry containing modified polyacrylic acid binder, and preparation method and application thereof |
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| CN202310665589.6A CN116759576B (en) | 2023-06-07 | 2023-06-07 | Lithium battery electrode coating slurry containing modified polyacrylic acid binder, and preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438727A (en) * | 2002-02-16 | 2003-08-27 | 三星Sdi株式会社 | Polymer electrolyte and lithium cell using same |
| CN104319367A (en) * | 2014-10-09 | 2015-01-28 | 奇瑞汽车股份有限公司 | Silicon/graphite composite anode material and preparation method thereof |
| CN109860596A (en) * | 2018-12-27 | 2019-06-07 | 上海三瑞高分子材料股份有限公司 | A kind of lithium battery silicon-based anode slurry and preparation method thereof |
-
2023
- 2023-06-07 CN CN202310665589.6A patent/CN116759576B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438727A (en) * | 2002-02-16 | 2003-08-27 | 三星Sdi株式会社 | Polymer electrolyte and lithium cell using same |
| CN104319367A (en) * | 2014-10-09 | 2015-01-28 | 奇瑞汽车股份有限公司 | Silicon/graphite composite anode material and preparation method thereof |
| CN109860596A (en) * | 2018-12-27 | 2019-06-07 | 上海三瑞高分子材料股份有限公司 | A kind of lithium battery silicon-based anode slurry and preparation method thereof |
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