CN114203967B - Preparation method of novel lithium ion battery negative electrode plate through colloid electrophoresis - Google Patents
Preparation method of novel lithium ion battery negative electrode plate through colloid electrophoresis Download PDFInfo
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- CN114203967B CN114203967B CN202111305177.9A CN202111305177A CN114203967B CN 114203967 B CN114203967 B CN 114203967B CN 202111305177 A CN202111305177 A CN 202111305177A CN 114203967 B CN114203967 B CN 114203967B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 65
- 238000001962 electrophoresis Methods 0.000 title claims abstract description 58
- 239000000084 colloidal system Substances 0.000 title claims abstract description 52
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 33
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 73
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 73
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 53
- 239000004094 surface-active agent Substances 0.000 claims abstract description 39
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- 230000008021 deposition Effects 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 57
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 56
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 claims description 44
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011889 copper foil Substances 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000003517 fume Substances 0.000 claims description 5
- 238000001652 electrophoretic deposition Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000005191 phase separation Methods 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 238000001502 gel electrophoresis Methods 0.000 claims 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 241001168730 Simo Species 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000005979 thermal decomposition reaction 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a novel lithium ion battery negative electrode plate by colloid electrophoresis, which relates to the technical field of lithium ion batteries and comprises a hard carbon negative electrode plate preparation step, a polyacid lithium salt preparation step, a surfactant and polyacid lithium salt synthesis step, a colloid solution preparation step and an electrophoresis deposition step.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a novel lithium ion battery negative electrode plate by colloid electrophoresis.
Background
Lithium ion batteries are common secondary batteries in the market, and the main application range is in power batteries, energy storage batteries and 3C products.
Lithium ion batteries operate primarily by virtue of lithium ions moving between a positive electrode and a negative electrode. During charge and discharge, li + With both electrodes being inserted and removed back and forth, li during charging + De-intercalation from the positive electrode, and intercalation into the negative electrode through the electrolyte, wherein the negative electrode is in a lithium-rich state; the opposite is true when discharging.
The hard carbon is a thermal decomposition of high molecular polymers, such as carbon, organic polymer pyrolytic carbon, carbon black and the like, and researches show that the hard carbon material has very high reversible specific capacity, generally 500-700 mAH, and the low or non-graphitized hard carbon is also a negative electrode material of a power lithium ion battery.
However, since the hard carbon has low gram capacity, the discharge voltage is greatly changed along with the capacity, and the first charge-discharge efficiency is lower than that of graphitized carbon, so that the hard carbon cannot be used in the field of lithium ion batteries on a large scale, and in order to fully exert the quick charge advantages of the hard carbon, the first efficiency is required to be improved, and the modification research on the hard carbon material is one of important ways for improving the hard carbon as a negative electrode lithium ion battery material.
The polyacid lithium salt colloid can improve the first efficiency of the battery due to the additional supplement of lithium ions, has larger surface area because the particle size of the colloid is positioned at the nanometer level, and is more compact and firm in SEI film formed on the surface of the negative electrode plate.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a novel pole piece preparation method which takes a traditional coated hard carbon pole piece as an electrophoresis substrate, deposits colloid synthesized by dioctadecyl dimethyl ammonium chloride (DODA) and polyacid lithium salt on the surface of the hard carbon pole piece in an ice bath in an electrophoresis manner, and forms a novel lithium ion battery pole piece.
The invention provides a preparation method of a novel lithium ion battery negative electrode plate by colloid electrophoresis, which comprises the following steps:
the preparation method comprises the steps of adopting a traditional preparation process of the hard carbon negative electrode plate of the lithium ion battery, coating hard carbon slurry on a copper foil current collector through a coating method, and drying the copper foil current collector through a drying oven of a coating machine to prepare the hard carbon negative electrode plate for later use;
the preparation method comprises the steps of preparing polyacid lithium salt, wherein polyacids with a classical keggin structure and sodium hydroxide react according to a molar ratio of 1:1 to obtain polyacid lithium salt serving as electrolyte;
in the step of preparing the polyacid lithium salt, the polyacid with a classical keggin structure refers to H 3 XY 12 O 40 Or H 4 XY 12 O 40 Wherein X is a silicon elementThe element Si or P, Y being tungsten element W or molybdenum element Mo, e.g. H 4 SiW 12 O 40 Correspondingly, the generated polyacid lithium salt is Li 4 SiW 12 O 40 。
A step of synthesizing a surfactant and a polyacid lithium salt, namely weighing the polyacid lithium salt prepared in the step of preparing the polyacid lithium salt and dioctadecyl dimethyl ammonium chloride (DODA) serving as the surfactant according to a molar ratio of 1:4, dissolving the weighed polyacid lithium salt in water, dissolving the weighed dioctadecyl dimethyl ammonium chloride (DODA) in chloroform, and respectively and uniformly stirring to prepare a solution; dropwise adding chloroform solution of dioctadecyl dimethyl ammonium chloride (DODA) into aqueous solution of polyacid lithium salt under stirring, separating chloroform phase to obtain solid, washing with deionized water, and volatilizing chloroform to obtain surfactant and polyacid lithium salt composition such as DODA-Li 4 SiW 12 O 40 ；
The synthesis step of the surfactant and the polyacid lithium salt is that a chloroform solution of dioctadecyl dimethyl ammonium chloride (DODA) is dripped into Li 4 SiW 12 O 40 Continuously stirring for at least 2 hours.
And synthesizing the surfactant and the polyacid lithium salt, namely washing the solid obtained after the chloroform phase separation with deionized water for at least 3 times.
A colloid solution preparation step, namely dissolving the surfactant and the polyacid lithium salt composition obtained in the surfactant and polyacid lithium salt synthesis step into Dimethylformamide (DMF) solution, and carrying out ultrasonic dissolution and ice bath stirring to obtain a milky colloid solution;
in the step of preparing the colloidal solution, ultrasonic dissolution is performed for at least 110 minutes, and ice bath stirring is performed for at least 2 hours.
And an electrophoretic deposition step, namely placing the hard carbon negative electrode plate prepared in the hard carbon negative electrode plate preparation step into the colloid solution prepared in the colloid solution preparation step for electrophoretic treatment to generate the negative electrode plate with the uniform film on the surface.
In the electrophoresis deposition step, a hard carbon negative electrode plate is used as a cathode, ITO glass is used as an anode, the electrophoresis voltage is 1-10V, the distance between the cathode and the anode is 1-3 cm, the electrophoresis time is 5-30 min, and the electrophoresis temperature is 2 ℃ in an ice bath environment to ensure that the solution is in a colloid state.
In the electrophoretic deposition step, after electrophoresis is finished, the negative electrode plate with the uniform film on the surface is dried at room temperature, and then is dried by a 60 ℃ oven.
Compared with the prior art, the invention uses the traditional coated hard carbon negative electrode plate as an electrophoresis substrate, and the colloid synthesized by dioctadecyl dimethyl ammonium chloride (DODA) and polyacid lithium salt is deposited on the surface of the hard carbon negative electrode plate in an ice bath in an electrophoresis mode to form the novel lithium ion battery negative electrode plate.
Drawings
The foregoing and the following detailed description of the invention will become more apparent when read in conjunction with the following drawings in which:
FIG. 1 is a schematic diagram of an electrophoresis process.
Detailed Description
The technical solution for achieving the object of the present invention will be further described with reference to several specific examples, but it should be noted that the technical solution claimed in the present invention includes but is not limited to the following examples.
Example 1
As a specific embodiment of the invention, the example discloses a preparation method of a novel lithium ion battery negative electrode plate of colloid electrophoresis, which comprises a hard carbon negative electrode plate preparation step, a polyacid lithium salt preparation step, a surfactant and polyacid lithium salt synthesis step, a colloid solution preparation step and an electrophoresis deposition step.
Specifically, the preparation step of the hard carbon negative electrode plate adopts the traditional preparation process of the lithium ion battery negative electrode plate, hard carbon slurry is coated on a copper foil current collector through a coating method, and the copper foil current collector is dried through a coating machine oven to prepare the hard carbon negative electrode plate for standby.
The polyacid lithium salt preparation step adopts polyacid H with classical keggin structure 4 SiW 12 O 40 Reacts with sodium hydroxide according to the mol ratio of 1:1 to obtain polyacid lithium salt Li as electrolyte 4 SiW 12 O 40 。
The step of synthesizing the surfactant and the polyacid lithium salt, namely the polyacid lithium salt Li prepared in the polyacid lithium salt preparation step 4 SiW 12 O 40 Weighing dioctadecyl dimethyl ammonium chloride (DODA) as surfactant according to a molar ratio of 1:4, and weighing lithium polyacid salt Li 4 SiW 12 O 40 Dissolving in water, dissolving weighed dioctadecyl dimethyl ammonium chloride (DODA) in chloroform, and respectively stirring uniformly to prepare solutions; dropwise adding a chloroform solution of dioctadecyl dimethyl ammonium chloride (DODA) to a polyacid lithium salt Li 4 SiW 12 O 40 After which the chloroform phase is separated to give a solid and washed with deionized water for at least 3 times, and the washed solid is placed in a fume hood to volatilize the chloroform clean to give a composition DODA-Li of surfactant and lithium polyacid salt 4 SiW 12 O 40 ；
The preparation step of the colloid solution comprises the steps of dissolving the synthesized product of the surfactant and the polyacid lithium salt, which is obtained in the synthesis step of the surfactant and the polyacid lithium salt, in a Dimethylformamide (DMF) solution, carrying out ultrasonic dissolution for at least 110 minutes and ice bath stirring for at least 2 hours to obtain a milky colloid solution;
and in the electrophoresis deposition step, as shown in fig. 1, the hard carbon negative electrode piece prepared in the hard carbon negative electrode piece preparation step is placed in the colloid solution prepared in the colloid solution preparation step for electrophoresis treatment, the hard carbon negative electrode piece is used as a cathode, ITO glass is used as an anode, the electrophoresis voltage is 1-10V, the distance between the cathode and the anode is 1-3 cm, the electrophoresis time is 5-30 min, the electrophoresis temperature is 2 ℃ in an ice bath environment to ensure that the solution is in a colloid state, a negative electrode piece with a uniform film on the surface is generated after electrophoresis, and the negative electrode piece with the uniform film on the surface is dried at room temperature and then is dried by a 60 ℃ oven to obtain the novel negative electrode piece I.
Example 2
As a further specific embodiment of the invention, the example discloses a preparation method of a novel lithium ion battery negative electrode plate of colloid electrophoresis, which comprises a hard carbon negative electrode plate preparation step, a polyacid lithium salt preparation step, a surfactant and polyacid lithium salt synthesis step, a colloid solution preparation step and an electrophoresis deposition step.
Specifically, the preparation step of the hard carbon negative electrode plate adopts the traditional preparation process of the lithium ion battery negative electrode plate, hard carbon slurry is coated on a copper foil current collector through a coating method, and the copper foil current collector is dried through a coating machine oven to prepare the hard carbon negative electrode plate for standby.
The polyacid lithium salt preparation step adopts polyacid H with classical keggin structure 4 SiW 12 O 40 Reacts with sodium hydroxide according to the mol ratio of 1:1 to obtain polyacid lithium salt Li as electrolyte 4 SiW 12 O 40 。
The step of synthesizing the surfactant and the polyacid lithium salt, namely the polyacid lithium salt Li prepared in the polyacid lithium salt preparation step 4 SiMo 12 O 40 Weighing dioctadecyl dimethyl ammonium chloride (DODA) as surfactant according to a molar ratio of 1:4, and weighing lithium polyacid salt Li 4 SiMo 12 O 40 Dissolving in water, dissolving weighed dioctadecyl dimethyl ammonium chloride (DODA) in chloroform, and respectively stirring uniformly to prepare solutions; dropwise adding a chloroform solution of dioctadecyl dimethyl ammonium chloride (DODA) to a polyacid lithium salt Li 4 SiMo 12 O 40 Is stirred continuously for at least 2 hours, then the chloroform phase is separated to obtain solid and is washed with deionized water for at least 3 times, and the washed solid is washedPlacing in a fume hood to volatilize chloroform to obtain DODA-Li as a composition of surfactant and polyacid lithium salt 4 SiMo 12 O 40 ；
The preparation step of the colloid solution comprises the steps of dissolving the synthesized product of the surfactant and the polyacid lithium salt, which is obtained in the synthesis step of the surfactant and the polyacid lithium salt, in a Dimethylformamide (DMF) solution, carrying out ultrasonic dissolution for at least 110 minutes and ice bath stirring for at least 2 hours to obtain a milky colloid solution;
and in the electrophoresis deposition step, as shown in fig. 1, the hard carbon negative electrode piece prepared in the hard carbon negative electrode piece preparation step is placed in the colloid solution prepared in the colloid solution preparation step for electrophoresis treatment, the hard carbon negative electrode piece is used as a cathode, ITO glass is used as an anode, the electrophoresis voltage is 3.8V, the distance between the cathode and the anode is 1-3 cm, the electrophoresis time is 5-30 min, the electrophoresis temperature is 2 ℃ in an ice bath environment to ensure that the solution is in a colloid state, a negative electrode piece with a uniform film on the surface is generated after electrophoresis, and after the negative electrode piece with the uniform film on the surface is dried at room temperature, the negative electrode piece is dried by a 60 ℃ oven to obtain the novel negative electrode piece II.
Example 3
As a further specific embodiment of the invention, the example discloses a preparation method of a novel lithium ion battery negative electrode plate of colloid electrophoresis, which comprises a hard carbon negative electrode plate preparation step, a polyacid lithium salt preparation step, a surfactant and polyacid lithium salt synthesis step, a colloid solution preparation step and an electrophoresis deposition step.
Specifically, the preparation step of the hard carbon negative electrode plate adopts the traditional preparation process of the lithium ion battery negative electrode plate, hard carbon slurry is coated on a copper foil current collector through a coating method, and the copper foil current collector is dried through a coating machine oven to prepare the hard carbon negative electrode plate for standby.
The polyacid lithium salt preparation step adopts polyacid H with classical keggin structure 3 PMo 12 O 40 Reacting with sodium hydroxide according to a molar ratio of 1:1 to obtain the polyacid lithium salt as electrolyteLi 3 PMo 12 O 40 。
The step of synthesizing the surfactant and the polyacid lithium salt, namely the polyacid lithium salt Li prepared in the polyacid lithium salt preparation step 3 PMo 12 O 40 Weighing dioctadecyl dimethyl ammonium chloride (DODA) as surfactant according to a molar ratio of 1:4, and weighing lithium polyacid salt Li 3 PMo 12 O 40 Dissolving in water, dissolving weighed dioctadecyl dimethyl ammonium chloride (DODA) in chloroform, and respectively stirring uniformly to prepare solutions; dropwise adding a chloroform solution of dioctadecyl dimethyl ammonium chloride (DODA) to a polyacid lithium salt Li 3 PMo 12 O 40 After which the chloroform phase is separated to give a solid and washed with deionized water for at least 3 times, and the washed solid is placed in a fume hood to volatilize the chloroform clean to give a composition DODA-Li of surfactant and lithium polyacid salt 3 PMo 12 O 40 ；
The preparation step of the colloid solution comprises the steps of dissolving the synthesized product of the surfactant and the polyacid lithium salt, which is obtained in the synthesis step of the surfactant and the polyacid lithium salt, in a Dimethylformamide (DMF) solution, carrying out ultrasonic dissolution for at least 110 minutes and ice bath stirring for at least 2 hours to obtain a milky colloid solution;
and in the electrophoresis deposition step, as shown in fig. 1, the hard carbon negative electrode piece prepared in the hard carbon negative electrode piece preparation step is placed in the colloid solution prepared in the colloid solution preparation step for electrophoresis treatment, the hard carbon negative electrode piece is used as a cathode, ITO glass is used as an anode, the electrophoresis voltage is 3.8V, the distance between the cathode and the anode is 1-3 cm, the electrophoresis time is 5-30 min, the electrophoresis temperature is 2 ℃ in an ice bath environment to ensure that the solution is in a colloid state, a negative electrode piece with a uniform film on the surface is generated after electrophoresis, and after the negative electrode piece with the uniform film on the surface is dried at room temperature, the negative electrode piece is dried by a 60 ℃ oven to obtain the novel negative electrode piece III.
Example 4
As the last specific embodiment of the invention, the example discloses a preparation method of a novel lithium ion battery negative electrode plate of colloid electrophoresis, which comprises a hard carbon negative electrode plate preparation step, a polyacid lithium salt preparation step, a surfactant and polyacid lithium salt synthesis step, a colloid solution preparation step and an electrophoresis deposition step.
Specifically, the preparation step of the hard carbon negative electrode plate adopts the traditional preparation process of the lithium ion battery negative electrode plate, hard carbon slurry is coated on a copper foil current collector through a coating method, and the copper foil current collector is dried through a coating machine oven to prepare the hard carbon negative electrode plate for standby.
The polyacid lithium salt preparation step adopts polyacid H with classical keggin structure 3 PW 12 O 40 Reacts with sodium hydroxide according to the mol ratio of 1:1 to obtain polyacid lithium salt Li as electrolyte 3 PW 12 O 40 。
The step of synthesizing the surfactant and the polyacid lithium salt, namely the polyacid lithium salt Li prepared in the polyacid lithium salt preparation step 3 PW 12 O 40 Weighing dioctadecyl dimethyl ammonium chloride (DODA) as surfactant according to a molar ratio of 1:4, and weighing lithium polyacid salt Li 3 PW 12 O 40 Dissolving in water, dissolving weighed dioctadecyl dimethyl ammonium chloride (DODA) in chloroform, and respectively stirring uniformly to prepare solutions; dropwise adding a chloroform solution of dioctadecyl dimethyl ammonium chloride (DODA) to a polyacid lithium salt Li 3 PW 12 O 40 After which the chloroform phase is separated to give a solid and washed with deionized water for at least 3 times, and the washed solid is placed in a fume hood to volatilize the chloroform clean to give a composition DODA-Li of surfactant and lithium polyacid salt 3 PW 12 O 40 ；
The preparation step of the colloid solution comprises the steps of dissolving the synthesized product of the surfactant and the polyacid lithium salt, which is obtained in the synthesis step of the surfactant and the polyacid lithium salt, in a Dimethylformamide (DMF) solution, carrying out ultrasonic dissolution for at least 110 minutes and ice bath stirring for at least 2 hours to obtain a milky colloid solution;
and in the electrophoresis deposition step, as shown in fig. 1, the hard carbon negative electrode piece prepared in the hard carbon negative electrode piece preparation step is placed in the colloid solution prepared in the colloid solution preparation step for electrophoresis treatment, the hard carbon negative electrode piece is used as a cathode, ITO glass is used as an anode, the electrophoresis voltage is 3.8V, the distance between the cathode and the anode is 1-3 cm, the electrophoresis time is 5-30 min, the electrophoresis temperature is 2 ℃ in an ice bath environment to ensure that the solution is in a colloid state, a negative electrode piece with a uniform film on the surface is generated after electrophoresis, and after the negative electrode piece with the uniform film on the surface is dried at room temperature, the negative electrode piece is dried by a 60 ℃ oven to obtain the novel negative electrode piece IV.
The obtained negative electrode tab i, negative electrode tab ii, negative electrode tab iii, negative electrode tab iv prepared in examples 1 to 4 above, and a hard carbon negative electrode tab prepared by the prior art method as a control group were assembled from lithium ion batteries, respectively, and then subjected to a first efficiency comparison test:
| pole piece | First time efficiency |
| Negative pole piece I | 93.0% |
| Negative pole piece II | 91.4% |
| Negative pole piece III | 92.1% |
| Negative pole piece IV | 91.3% |
| Control group | 88.2% |
The test result shows that the novel lithium battery negative electrode plate prepared by the method has obviously improved first efficiency and stability compared with the product prepared by the prior method.
Claims (7)
1. The preparation method of the novel lithium ion battery negative electrode plate by colloid electrophoresis is characterized by comprising the following steps of:
the preparation method comprises the steps of coating hard carbon slurry on a copper foil current collector through a coating method, and drying the copper foil current collector through a coating machine oven to prepare the hard carbon negative electrode plate for later use;
the preparation method comprises the steps of preparing polyacid lithium salt, wherein polyacids with a classical keggin structure and sodium hydroxide react according to a molar ratio of 1:1 to obtain polyacid lithium salt serving as electrolyte;
a step of synthesizing a surfactant and a polyacid lithium salt, namely weighing the polyacid lithium salt prepared in the step of preparing the polyacid lithium salt and dioctadecyl dimethyl ammonium chloride (DODA) serving as the surfactant according to a molar ratio of 1:4, dissolving the weighed polyacid lithium salt in water, dissolving the weighed dioctadecyl dimethyl ammonium chloride (DODA) in chloroform, and respectively and uniformly stirring to prepare a solution; dropwise adding a chloroform solution of dioctadecyl dimethyl ammonium chloride (DODA) into an aqueous solution of a polyacid lithium salt and continuously stirring, separating chloroform phases to obtain a solid, washing the solid with deionized water, and placing the solid in a fume hood to volatilize the chloroform cleanly to obtain a composition of a surfactant and the polyacid lithium salt;
a colloid solution preparation step, namely dissolving the surfactant and the polyacid lithium salt composition obtained in the surfactant and polyacid lithium salt synthesis step into Dimethylformamide (DMF) solution, and carrying out ultrasonic dissolution and ice bath stirring to obtain a milky colloid solution;
and an electrophoretic deposition step, namely placing the hard carbon negative electrode plate prepared in the hard carbon negative electrode plate preparation step into the colloid solution prepared in the colloid solution preparation step for electrophoretic treatment to generate the negative electrode plate with the uniform film on the surface.
2. The method for preparing the novel lithium ion battery negative electrode plate by colloid electrophoresis as claimed in claim 1, wherein the method comprises the following steps: in the step of preparing the polyacid lithium salt, the polyacid with a classical keggin structure refers to H 3 XY 12 O 40 Or H 4 XY 12 O 40 Wherein X is silicon element Si or phosphorus element P, Y is tungsten element W or molybdenum element Mo.
3. The method for preparing the novel lithium ion battery negative electrode plate by colloid electrophoresis as claimed in claim 1, wherein the method comprises the following steps: the synthesis step of the surfactant and the polyacid lithium salt is that a chloroform solution of dioctadecyl dimethyl ammonium chloride (DODA) is dripped into Li 4 SiW 12 O 40 Continuously stirring for at least 2 hours.
4. The method for preparing the novel lithium ion battery negative electrode plate by using the gel electrophoresis as claimed in claim 1 or 2, which is characterized by comprising the following steps of: and synthesizing the surfactant and the polyacid lithium salt, namely washing the solid obtained after the chloroform phase separation with deionized water for at least 3 times.
5. The method for preparing the novel lithium ion battery negative electrode plate by colloid electrophoresis as claimed in claim 1, wherein the method comprises the following steps: in the step of preparing the colloidal solution, ultrasonic dissolution is performed for at least 110 minutes, and ice bath stirring is performed for at least 2 hours.
6. The method for preparing the novel lithium ion battery negative electrode plate by colloid electrophoresis as claimed in claim 1, wherein the method comprises the following steps: in the electrophoresis deposition step, a hard carbon negative electrode plate is used as a cathode, ITO glass is used as an anode, the electrophoresis voltage is 1-10V, the distance between the cathode and the anode is 1-3 cm, the electrophoresis time is 5-30 min, and the electrophoresis temperature is 2 ℃ in an ice bath environment.
7. The method for preparing the novel lithium ion battery negative electrode plate by using the gel electrophoresis as defined in claim 1 or 6, which is characterized by comprising the following steps of: in the electrophoretic deposition step, after electrophoresis is finished, the negative electrode plate with the uniform film on the surface is dried at room temperature, and then is dried by a 60 ℃ oven.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111305177.9A CN114203967B (en) | 2021-11-05 | 2021-11-05 | Preparation method of novel lithium ion battery negative electrode plate through colloid electrophoresis |
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| CN202111305177.9A CN114203967B (en) | 2021-11-05 | 2021-11-05 | Preparation method of novel lithium ion battery negative electrode plate through colloid electrophoresis |
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| Publication Number | Publication Date |
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| CN114203967A CN114203967A (en) | 2022-03-18 |
| CN114203967B true CN114203967B (en) | 2024-03-15 |
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| CN110085791A (en) * | 2019-04-11 | 2019-08-02 | 电子科技大学 | A kind of lithium ion battery separator and preparation method thereof |
| CN112042031A (en) * | 2018-05-07 | 2020-12-04 | I-Ten公司 | Solid electrolyte for electrochemical device |
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