CN114221045B - Preparation method of porous carbon lithium supplementing negative electrode piece lithium ion battery - Google Patents
Preparation method of porous carbon lithium supplementing negative electrode piece lithium ion battery Download PDFInfo
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- CN114221045B CN114221045B CN202111304384.2A CN202111304384A CN114221045B CN 114221045 B CN114221045 B CN 114221045B CN 202111304384 A CN202111304384 A CN 202111304384A CN 114221045 B CN114221045 B CN 114221045B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 78
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 71
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 51
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 50
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 title claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 112
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 108
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 108
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 60
- 238000000576 coating method Methods 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 9
- 238000005507 spraying Methods 0.000 claims abstract description 6
- 238000000151 deposition Methods 0.000 claims abstract description 4
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims description 30
- 239000000853 adhesive Substances 0.000 claims description 20
- 230000001070 adhesive effect Effects 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- 239000011267 electrode slurry Substances 0.000 claims description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000004966 Carbon aerogel Substances 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 150000002642 lithium compounds Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 239000003292 glue Substances 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 229920006037 cross link polymer Polymers 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- 238000009461 vacuum packaging Methods 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000006183 anode active material Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 claims description 2
- MNLNJNKIBQPPAB-UHFFFAOYSA-N [O-2].[Mn+2].[Al+3].[Ni+2].[Li+].[O-2].[O-2].[O-2] Chemical compound [O-2].[Mn+2].[Al+3].[Ni+2].[Li+].[O-2].[O-2].[O-2] MNLNJNKIBQPPAB-UHFFFAOYSA-N 0.000 claims description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 2
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 2
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims description 2
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 claims description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims 1
- 239000004584 polyacrylic acid Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 230000007704 transition Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract description 2
- 239000007888 film coating Substances 0.000 abstract description 2
- 238000009501 film coating Methods 0.000 abstract description 2
- 230000008595 infiltration Effects 0.000 abstract description 2
- 238000001764 infiltration Methods 0.000 abstract description 2
- 238000006138 lithiation reaction Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 8
- 239000013589 supplement Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 3
- 239000006256 anode slurry Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009469 supplementation Effects 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a porous carbon lithium-supplementing negative electrode piece lithium ion battery, and relates to the technical field of lithium ion battery electrode materials. According to the invention, the cross-linked high polymer polyvinyl alcohol mixed with the porous carbon material is coated on the negative electrode plate of the lithium ion battery, and the lithium supplementing agent is filled into the pore diameter of the porous carbon in the cross-linked grid by a coating method, a magnetron sputtering deposition method or a spraying film coating method, so that the accurate and controllable lithium supplementing of the negative electrode is realized, and the lithium precipitation phenomenon of the negative electrode caused by transition lithiation is prevented. The selected porous carbon can 'tie' redundant lithium powder in the pore wall, and lithium is supplemented in the reaction stage, the lithium powder distributed on the surface of the porous carbon is mainly supplemented in the initial stage, and when the battery is charged and discharged in a certain stage, along with the increase of the internal temperature of the battery, the activation energy is increased, and the lithium powder tied in the pore diameter is continuously used for supplementing lithium. On the other hand, the abundant pore diameters of the porous carbon can also accelerate the infiltration of the electrolyte in the battery, increase the adsorption of the electrolyte and prevent the electrolyte from drying up.
Description
Technical Field
The invention relates to the technical field of electrode materials of lithium ion batteries, in particular to a preparation method of a porous carbon lithium supplementing negative electrode piece lithium ion battery.
Background
In the first-week charging process of the lithium ion battery, a solid electrolyte membrane (SEI film) is formed on the surface of the negative electrode, about 10% of active lithium in the positive electrode is consumed, irreversible capacity loss is caused, and the energy density of the lithium ion battery is further reduced. In order to ensure the capacity of the battery, the lost lithium needs to be supplemented, and the technology is pre-lithium, so that the pre-lithium technology can not only compensate the first-effect loss of the anode, but also provide an additional lithium source, thereby being beneficial to improving the energy density and the cycle performance of the ion battery.
At present, lithium supplementing methods are classified into positive electrode lithium supplementing and negative electrode lithium supplementing. Among them, negative electrode lithium-supplementing, such as lithium powder lithium-supplementing and lithium foil lithium-supplementing, are most commonly used, and are also the most fundamentally solving problems, and positive electrode lithium-supplementing can only increase by several hundred times in cycle life. However, the process of the negative electrode lithium supplementing technology tends to cause a large amount of heat generation, the process control is difficult, meanwhile, the traditional negative electrode hot-pressing lithium belt or lithium foil and other modes are adopted to easily generate negative electrode transition lithium supplementing, and potential safety hazards are generated due to lithium precipitation.
In the prior art, chinese patent publication No. CN112397682A discloses a negative electrode plate subjected to lithium supplementing treatment and a lithium ion battery thereof. According to the technical scheme, the problem of heating of the pole piece is effectively solved, the channel formed by the lithium supplementing area and the gap area can enable the lithium ion battery to be soaked in the electrolyte more effectively after the lithium ion battery is injected, the energy density of the battery is improved, and meanwhile the cycle life and the dynamic performance of the battery can be prolonged. However, the intermittent control method has complex process and difficult large-scale application by intermittently reserving white lithium on the surface of the negative electrode layer to ensure that the negative electrode layer is distributed by a lithium supplementing region and a non-lithium supplementing region.
The Chinese patent with publication number of CN112599723A discloses a lithium supplementing negative electrode plate, a preparation method thereof and a lithium ion battery. The method is complex in process, high in pore-forming cost, and the pore diameter of the copper foil current collector perforated by the method is not abundant and the lithium supplementing effect is not good.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a porous carbon lithium supplementing negative electrode piece lithium ion battery, which is characterized in that 'Kong Shuli' lithium supplementing is carried out by utilizing a porous active carbon coating, active lithium is uniformly filled into the porous active carbon, uniform and accurate lithium supplementing is realized, the cost is low, and the large-scale production is easy.
In order to achieve the above purpose, the present invention adopts the technical scheme that:
the preparation method of the lithium ion battery with the porous carbon lithium supplementing negative electrode plate comprises the steps of preparing the lithium supplementing negative electrode plate, preparing the positive electrode plate and preparing the lithium ion battery;
s1, preparation of lithium supplementing negative electrode plate
The preparation method of the lithium supplementing negative electrode plate comprises the steps of preparing a negative electrode body, preparing a porous carbon coating, preparing a lithium supplementing agent and preparing the negative electrode plate.
S11, preparing a cathode body: and mixing and stirring the anode active material, the conductive agent, the first adhesive and the first solvent to obtain anode slurry, and coating and drying the anode slurry after the viscosity of the anode slurry is regulated to obtain an anode body.
In the preparation of the anode body, the anode active material comprises one or more of artificial graphite, natural graphite, mesophase carbon microspheres, soft carbon and hard carbon.
S12, preparing a porous carbon coating: and mixing and dispersing the porous carbon material, the cross-linked polymer polyvinyl alcohol, the second adhesive and the second solvent to prepare a porous carbon glue solution, and coating the porous carbon glue solution on the negative electrode body obtained in the preparation of the negative electrode body to obtain the negative electrode body containing the porous carbon.
In the preparation of the porous carbon coating, the mass percentage of the porous carbon material is 5-50%. Preferably, the mass percentage of the porous carbon material is 10-30%.
In the preparation of the porous carbon coating, the porous carbon material comprises one or more of porous activated carbon, porous carbon nanotubes, porous carbon fibers and porous carbon aerogel. The composite carbon material of the type has rich pore diameter. Preferably, the porous carbon material is porous activated carbon, and the cost is low.
In the preparation of the porous carbon coating, the porosity of the porous carbon material is 30-90%. Preferably, the porosity of the porous carbon material is 30-60%. Because the porosity is rich, the specific surface area is too large, the first effect loss is too large, the consumed adhesive is too much, and the internal resistance of the battery is increased, therefore, the invention reduces the maximum value to 30-60 percent on the basis of 30-90 percent.
In the preparation of the porous carbon coating, the pore diameter of the porous carbon material is 10-100 nm. Preferably, the pore size of the porous carbon material is 50-80 nm.
S13, preparation of a lithium supplementing agent: dispersing simple substance lithium powder or lithium compound and a third adhesive into a third solvent to prepare the lithium supplementing emulsion.
In the preparation of the lithium supplementing agent, the mass percentage of the simple substance lithium powder or the lithium compound is 5-90%. Preferably, the mass percentage of the simple substance lithium powder or the lithium compound is 20-50%.
In the preparation of the lithium supplementing agent, the lithium compound comprises lithium oxide, lithium nitride, lithium sulfide and Li 5 FeO 4 、Li 6 CoO 4 One or more of lithium hydroxide and lithium carbonate.
In the preparation of the cathode body, the preparation of the porous carbon coating and the preparation of the lithium supplementing agent, the first adhesive, the second adhesive and the third adhesive are one of polyacrylic acid (PAA), polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), polyacrylonitrile (PAN) and Styrene Butadiene Rubber (SBR); the first solvent, the second solvent and the third solvent are all N-methylpyrrolidone (NMP).
S14, preparing a negative electrode plate: filling and dispersing the lithium supplementing emulsion prepared in the preparation of the lithium supplementing agent into the surface or aperture of porous carbon in the cross-linked network on the anode body prepared in the preparation of the porous carbon coating by a coating, magnetron sputtering deposition or spraying coating method to obtain the lithium supplementing anode piece.
In the preparation of the lithium supplementing agent, the thickness of the double-sided spraying of the negative electrode plate is 2-4um.
S2, preparing a positive pole piece
And mixing the positive electrode material, the second conductive agent and the fourth adhesive, stirring and homogenizing under the action of a vacuum stirrer to obtain positive electrode slurry of the lithium ion battery with certain viscosity, uniformly coating the positive electrode slurry on two surfaces of an aluminum foil of a positive electrode current collector, and drying to obtain a positive electrode plate.
In the preparation step of the positive electrode sheet, the positive electrode material comprises a positive electrode current collector and a positive electrode active substance, wherein the positive electrode active substance comprises one or more of lithium iron phosphating, lithium cobalt oxide, lithium manganese oxide, lithium nickel manganese oxide, lithium manganese nickel aluminum oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide and lithium transition metal oxide.
S3, lithium ion battery preparation steps
And separating the lithium-supplementing negative electrode piece obtained in the lithium-supplementing negative electrode piece preparation step and the positive electrode piece obtained in the positive electrode piece preparation step by using a diaphragm, winding the positive electrode piece and the lithium-supplementing negative electrode piece to obtain a bare cell, packaging the bare cell by using a shell, drying, injecting electrolyte, and carrying out vacuum packaging, standing, formation and shaping procedures to obtain the lithium ion battery.
In the lithium ion battery preparation step, the separator comprises one or more of Polyethylene (PE), polypropylene (PP), polypropylene/polyethylene/polypropylene (PP/PE/PP three-layer composite separator), polytetrafluoroethylene, polyimide and ceramic-coated polyolefin separator.
The lithium ion battery prepared by the preparation method comprises a positive electrode plate, a lithium supplementing negative electrode plate, a diaphragm for separating the positive electrode plate from the lithium supplementing negative electrode plate, a shell and electrolyte filled in the shell and used for conducting ions between the positive electrode plate and the negative electrode plate.
The lithium supplementing negative electrode piece comprises a negative electrode body, a porous active carbon layer coated on the surface of the negative electrode body and with cross-linked polymer dispersed, and a lithium supplementing agent uniformly filled on the porous active carbon layer.
The invention has the beneficial effects that:
compared with the prior art, the method has the advantages that the cross-linked high polymer polyvinyl alcohol mixed with the porous carbon material is coated on the negative electrode plate of the lithium ion battery, and the lithium supplementing agent is filled into the pore diameter of the porous carbon in the cross-linked grid through a coating method, a magnetron sputtering deposition method or a spraying film coating method, so that the accurate and controllable lithium supplementing of the negative electrode is realized, and the phenomenon of lithium precipitation of the negative electrode due to transition lithiation is prevented. The selected porous carbon can 'tie' redundant lithium powder in the pore wall, and lithium is supplemented in the reaction stage, the lithium powder distributed on the surface of the porous carbon is mainly supplemented in the initial stage, and when the battery is charged and discharged in a certain stage, along with the increase of the internal temperature of the battery, the activation energy is increased, and the lithium powder tied in the pore diameter is continuously used for supplementing lithium. On the other hand, the abundant pore diameters of the porous carbon can also accelerate the infiltration of electrolyte in the battery, increase the adsorption of the electrolyte, prevent the electrolyte from drying up and prolong the cycle life of the battery. In addition, the invention coats the cross-linked high polymer polyvinyl alcohol mixed with porous carbon on the surface of the negative electrode, and then coats the lithium glue solution, thereby having simple preparation process and easy mass production.
Drawings
FIG. 1 is a schematic diagram showing the distribution of the negative electrode, porous carbon and lithium-supplementing agent of the battery;
fig. 2 is a comparison of the cycle diagrams of the cells of the present invention.
Detailed Description
The conception, specific structure, and technical effects produced by the present invention will be clearly and completely described below with reference to the embodiments and the drawings to fully understand the objects, features, and effects of the present invention.
Example 1
A preparation method of a lithium ion battery with a lithium-supplementing porous carbon negative electrode plate comprises a preparation step of the lithium-supplementing negative electrode plate, a preparation step of a positive electrode plate and a preparation step of the lithium ion battery.
1. Preparation of lithium supplementing negative electrode plate
(1) Preparing a cathode body: according to the weight percentage of 95 percent to 2.5 percent and 2.5 percent, the artificial graphite, the acetylene black and the PVDF are dispersed in the solvent NMP, the mixture is stirred for 4 hours to obtain negative electrode slurry, the negative electrode slurry is regulated to have the solid content of 50 percent, the viscosity of 4700 mpa.s and the fineness of the negative electrode slurry of 35um, and the negative electrode body is obtained by coating and drying.
(2) Preparing a porous carbon coating: the porous activated carbon material is mixed and dispersed according to the mass percentage of slurry of 10%, the cross-linked polymer PVA of 20%, the adhesive of 2% and the NMP solvent according to a certain proportion to prepare porous carbon glue solution, and the porous glue solution is coated on the cathode body prepared in the step (1).
(3) And (3) preparation of a lithium supplementing agent: and dispersing the simple substance lithium powder into a solvent NMP according to the mass percentage of 20% and 3% of an adhesive to prepare the lithium supplementing emulsion.
(4) Preparation of a 'Kong Shuli' negative electrode plate: filling the lithium supplementing agent coating liquid prepared in the step (3) into the surface or the aperture of the porous carbon of the cathode body in the step (2) by using a coating method, wherein the thickness of the double-sided lithium supplementing coating is 4um.
2. Preparation of positive pole piece
Mixing the positive electrode active material, the conductive agent and the adhesive according to the mass ratio of 96:2:2, stirring and homogenizing under the action of a vacuum stirrer to obtain positive electrode slurry of the lithium ion battery with certain viscosity, uniformly coating the positive electrode slurry on two surfaces of an aluminum foil of a positive electrode current collector, and drying at 85 ℃ to obtain a positive electrode plate.
3. Lithium ion battery preparation
Separating the 'Kong Shuli' negative electrode plate obtained in the first step and the positive electrode plate obtained in the second step by using a polyolefin isolating film, winding to obtain a bare cell, packaging the bare cell by using a shell, drying, injecting electrolyte, and carrying out the procedures of vacuum packaging, standing, formation, shaping and the like to obtain the lithium ion battery.
The lithium ion battery prepared by the preparation method comprises a positive electrode plate, a lithium supplementing negative electrode plate, a diaphragm for separating the positive electrode plate from the lithium supplementing negative electrode plate, a shell and electrolyte filled in the shell and used for conducting ions between the positive electrode plate and the negative electrode plate.
The lithium supplementing negative electrode piece comprises a negative electrode body, a porous active carbon layer coated on the surface of the negative electrode body and with cross-linked polymer dispersed, and a lithium supplementing agent uniformly filled on the porous active carbon layer, as shown in figure 1.
Example 2
In this example, the mass ratio of the porous activated carbon in (2) and the double-sided lithium supplementing thickness in (4) were adjusted to 20% of the porous carbon slurry in the preparation of the lithium supplementing negative electrode sheet of example 1, and all the other steps were the same as those in example 1.
Example 3
In this example, the mass ratio of the porous activated carbon in (2) and the double-sided lithium supplementing thickness in (4) were adjusted to 30% of the porous carbon slurry in the preparation of the lithium supplementing negative electrode sheet of example 1, and all the other steps were the same as those in example 1.
Example 4
In this example, the porous activated carbon in (2) in the preparation of the lithium-compensating negative electrode sheet of example 1 was replaced with a porous Carbon Nanotube (CNT), the mass percentage of which is 10% of that of the porous carbon slurry, and the thickness of the double-sided lithium-compensating sheet in (4) was 4um, and all the other steps were the same as those in example 1.
Example 5
In this example, the porous activated carbon in (2) in the preparation of the lithium-compensating negative electrode sheet in example 1 was replaced with a porous Carbon Nanotube (CNT), the mass percentage of which is 20% of that of the porous carbon slurry, and the thickness of the double-sided lithium-compensating sheet in (4) was 3um, and all the other steps were the same as those in example 1.
Example 6
In this embodiment, the porous activated carbon in (2) in the preparation of the lithium-supplementing negative electrode sheet in example 1 is replaced by porous carbon fiber, the mass percentage of the porous activated carbon is 10% of that of the porous carbon slurry, the thickness of the double-sided lithium supplement in (4) is 4um, and all the other steps are the same as those in example 1.
Example 7
In this embodiment, the porous activated carbon in (2) in the preparation of the lithium-supplementing negative electrode sheet in example 1 is replaced by porous carbon fiber, the mass percentage of the porous activated carbon is 20% of that of the porous carbon slurry, the thickness of the double-sided lithium supplement in (4) is 3um, and all the other steps are the same as those in example 1.
Example 8
In the embodiment, the porous activated carbon in the preparation of the lithium-supplementing negative electrode sheet in the embodiment 1 is replaced by porous carbon aerogel, the mass percentage of the porous activated carbon is 10% of that of the porous carbon slurry, the lithium-supplementing agent in the embodiment 3 is lithium powder, the thickness of the double-sided lithium-supplementing agent in the embodiment 4 is 4um, and all other steps are the same as those in the embodiment 1.
Example 9
In this embodiment, the porous activated carbon in (2) in the preparation of the lithium-supplementing negative electrode sheet in example 1 is replaced by porous carbon aerogel, the mass percentage of the porous carbon aerogel is 10% of that of the porous carbon slurry, the lithium-supplementing agent in (3) is replaced by lithium sulfide, the thickness of double-sided lithium supplementing is 4um, and all the other steps are the same as those in example 1.
Example 10
In the embodiment, the porous activated carbon in the preparation of the lithium-supplementing negative electrode sheet in the embodiment 1 is changed into porous carbon aerogel, the mass percentage of the porous activated carbon is 10% of that of the porous carbon slurry, the lithium-supplementing agent in the embodiment 3 is changed into lithium oxide, the thickness of the double-sided lithium supplement in the embodiment 4 is 4um, and all other steps are the same as those in the embodiment 1.
Example 11
In the embodiment, the porous activated carbon in the preparation of the lithium-supplementing negative electrode sheet in the embodiment 1 is replaced by porous carbon aerogel, the mass percentage of the porous activated carbon is 10% of that of the porous carbon slurry, the lithium-supplementing agent in the embodiment 3 is replaced by lithium nitride, the thickness of the double-sided lithium supplement in the embodiment 4 is 4um, and all other steps are the same as those in the embodiment 1.
Comparative example 1
The first step: preparation of lithium-supplementing negative electrode sheet "Kong Shuli" preparation of negative electrode sheet:
dispersing artificial graphite, acetylene black and PVDF in a solvent NMP according to the weight percentage of 95 percent to 2.5 percent and 2.5 percent, stirring for 4 hours to obtain negative electrode slurry, adjusting the solid content of the negative electrode to 50 percent, the viscosity to 4700 mpa.s, and the fineness of the negative electrode slurry to be about 35um; dispersing 20% of simple substance lithium powder and 3% of adhesive into a solvent NMP according to mass percentage to prepare lithium supplementing emulsion; filling the lithium supplementing agent coating liquid into the surface or aperture of the porous carbon of the negative electrode plate by using a coating method.
And a second step of: preparation of positive pole piece
Mixing the positive electrode active material, the conductive agent and the adhesive according to the mass ratio of 96:2:2, stirring and homogenizing under the action of a vacuum stirrer to obtain positive electrode slurry of the lithium ion battery with certain viscosity, uniformly coating the positive electrode slurry on two surfaces of an aluminum foil of a positive electrode current collector, and drying at 85 ℃ to obtain a positive electrode plate.
And a third step of: preparation of a lithium ion battery:
separating the first step 'Kong Shuli' negative pole piece and the second step positive pole piece by using a polyolefin isolating film, winding to obtain a bare cell, packaging the bare cell by using a shell, drying, injecting electrolyte, and carrying out the procedures of vacuum packaging, standing, formation, shaping and the like to obtain the lithium ion battery.
Comparative example 2
The first step: dispersing artificial graphite, acetylene black and PVDF in a solvent NMP according to the weight percentage of 95 percent to 2.5 percent and 2.5 percent, stirring for 4 hours to obtain negative electrode slurry, adjusting the solid content of the negative electrode to 50 percent, the viscosity to 4700 mpa.s, and the fineness of the negative electrode slurry to about 35um; coating to obtain the negative electrode plate.
The second and third steps were the same as in comparative example 1, and the battery was assembled in a general lithium ion battery assembly manner.
The lithium batteries prepared in examples 1 to 11 and comparative examples 1 to 2 were subjected to charge and discharge test after formation and activation, and lithium supplementing parameters and cell performance data are shown in the following table 1.
Table 1 parameters of lithium supplementation of pole pieces and electrochemical properties of corresponding batteries
The test results in table 1 show that, compared with comparative example 2, the first coulombic efficiency of the lithium-supplementing negative electrode sheet is obviously superior to that of the non-lithium-supplementing negative electrode sheet, mainly because the lithium-supplementing layers on the inner and outer surfaces of the porous carbon supplement lithium ions Li+ consumed in the SEI film forming process, in addition, the 1000-cycle capacity retention rate of the battery is greatly improved compared with that of the non-lithium-supplementing negative electrode material battery along with the increase of the cycle times, and the lithium-supplementing agent bound in the pore diameter of the porous carbon material continuously outputs, supplements lithium ions of the positive electrode material, reduces the consumption of lithium ions of the positive electrode, ensures that the positive electrode material is efficiently utilized, and prolongs the service life of the battery.
In addition, as can be seen from the comparison of examples 1 to 11, porous carbon, carbon nanotubes, carbon aerogel and carbon fibers are not greatly different in performance, and the porous activated carbon is economical from the viewpoint of cost, on the other hand, from the viewpoint of lithium supplement reagent comparison, the lithium powder is the best lithium supplement reagent relative to the lithium compound, apart from the safety factor.
Comparative examples 1 and 2 can show that the porous carbon gel layer between the negative electrode layer and the lithium supplementing layer has a Kong Shuli effect, the battery performance difference is large, the Kong Shuli carbon layer can accurately control the amount of lithium and control the lithium supplementing speed, local overheating is prevented, the temperature is raised too fast, the phenomenon of lithium enrichment and lithium precipitation occurs, and dendrites penetrate through the diaphragm to generate potential safety hazards.
Comparison of the battery cycle graphs of example 1, example 5 and comparative example 2 as shown in fig. 2, the a curve is the variation of the battery capacity of example 1 with the increase of the cycle number, the b curve is the variation of the battery capacity of example 5 with the increase of the cycle number, and the c curve is the variation of the battery capacity of comparative example 1 with the increase of the cycle number, and it can be seen from the graph that the battery capacities of the porous carbon lithium-ion battery of examples 1 and 5 of the present invention are superior to the battery capacity of comparative example 2 with the increase of the cycle number.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the embodiments described above, and various equivalent modifications and substitutions can be made by those skilled in the art without departing from the spirit of the present invention, and these are intended to be included in the scope of the present invention as defined in the appended claims.
Claims (9)
1. A preparation method of a porous carbon lithium supplementing negative electrode piece lithium ion battery is characterized by comprising the following steps: the method comprises a lithium supplementing negative electrode plate preparation step, a positive electrode plate preparation step and a lithium ion battery preparation step;
the preparation steps of the lithium supplementing negative electrode plate comprise:
preparing a cathode body: mixing and stirring a negative electrode active material, a conductive agent, a first adhesive and a first solvent to obtain negative electrode slurry, and coating and drying the negative electrode slurry after viscosity adjustment to obtain a negative electrode body;
preparing a porous carbon coating: mixing and dispersing a porous carbon material, a cross-linked polymer polyvinyl alcohol, a second adhesive and a second solvent to prepare a porous carbon glue solution, and coating the porous carbon glue solution on a negative electrode body prepared in the preparation of the negative electrode body to obtain a negative electrode body containing porous carbon;
and (3) preparation of a lithium supplementing agent: dispersing simple substance lithium powder or lithium compound and a third adhesive into a third solvent to prepare lithium supplementing emulsion;
preparing a negative electrode plate: filling and dispersing the lithium supplementing emulsion prepared in the preparation of the lithium supplementing agent into the surface or aperture of porous carbon in a cross-linked network on a cathode body prepared in the preparation of the porous carbon coating by a coating, magnetron sputtering deposition or spraying film plating method to obtain a lithium supplementing cathode pole piece; wherein, the thickness of the double-sided spraying of the negative electrode plate is 2-4um;
the preparation method comprises the steps of mixing a positive electrode material, a second conductive agent and a fourth adhesive, stirring and homogenizing under the action of a vacuum stirrer to obtain positive electrode slurry of the lithium ion battery with certain viscosity, uniformly coating the positive electrode slurry on two surfaces of an aluminum foil of a positive electrode current collector, and drying to obtain the positive electrode sheet;
and the lithium ion battery preparation step is that the lithium-supplementing negative electrode plate obtained in the lithium-supplementing negative electrode plate preparation step and the positive electrode plate obtained in the positive electrode plate preparation step are separated by a diaphragm, the positive electrode plate and the lithium-supplementing negative electrode plate are wound to obtain a bare cell, the bare cell is packaged by a shell, electrolyte is injected after drying, and the lithium ion battery is obtained through vacuum packaging, standing, formation and shaping procedures.
2. The method for preparing a lithium ion battery according to claim 1, wherein: in the preparation of the anode body, the anode active material comprises one or more of artificial graphite, natural graphite, mesophase carbon microspheres, soft carbon and hard carbon.
3. The method for preparing a lithium ion battery according to claim 1, wherein: in the preparation of the porous carbon coating, the porous carbon material comprises one or more of porous activated carbon, porous carbon nanotubes, porous carbon fibers and porous carbon aerogel.
4. The method for preparing a lithium ion battery according to claim 1, wherein: in the preparation of the porous carbon coating, the mass percentage of the porous carbon material is 5-50%, the porosity is 30-90%, and the pore diameter is 10-100 nm.
5. The method for preparing a lithium ion battery according to claim 1, wherein: in the preparation of the lithium supplementing agent, the mass percentage of the simple substance lithium powder or the lithium compound is 5-90%.
6. The method for preparing a lithium ion battery according to claim 1, wherein: in the preparation of the lithium supplementing agent, the lithium compound comprises lithium oxide, lithium nitride, lithium sulfide and Li 5 FeO 4 、Li 6 CoO 4 One or more of lithium hydroxide and lithium carbonate.
7. The method for preparing a lithium ion battery according to claim 1, wherein: in the preparation of the cathode body, the preparation of the porous carbon coating and the preparation of the lithium supplementing agent, the first adhesive, the second adhesive and the third adhesive are one of polyacrylic acid, polyethylene oxide, polyvinylidene fluoride, polyvinyl alcohol, polyacrylonitrile and styrene butadiene rubber; the first solvent, the second solvent and the third solvent are all N-methylpyrrolidone.
8. The method for preparing a lithium ion battery according to claim 1, wherein: in the preparation step of the positive electrode sheet, the positive electrode material comprises a positive electrode current collector and a positive electrode active substance, wherein the positive electrode active substance comprises one or more of lithium iron phosphide, lithium cobalt oxide, lithium manganese oxide, lithium nickel manganese oxide, lithium manganese nickel aluminum oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide and lithium transition metal oxide.
9. The method for preparing a lithium ion battery according to claim 1, wherein: in the lithium ion battery preparation step, the separator comprises one or more of polyethylene, polypropylene/polyethylene/polypropylene three-layer composite separator, polytetrafluoroethylene, polyimide and ceramic-coated polyolefin separator.
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