CN114221045A - Preparation method of porous carbon lithium-supplement negative electrode sheet lithium ion battery - Google Patents
Preparation method of porous carbon lithium-supplement negative electrode sheet lithium ion battery Download PDFInfo
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- CN114221045A CN114221045A CN202111304384.2A CN202111304384A CN114221045A CN 114221045 A CN114221045 A CN 114221045A CN 202111304384 A CN202111304384 A CN 202111304384A CN 114221045 A CN114221045 A CN 114221045A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000013589 supplement Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 76
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 59
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 41
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 119
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 119
- 238000000576 coating method Methods 0.000 claims abstract description 39
- 239000011248 coating agent Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 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
- 230000008021 deposition Effects 0.000 claims abstract description 4
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 4
- 239000000853 adhesive Substances 0.000 claims description 20
- 230000001070 adhesive effect Effects 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 17
- 230000001502 supplementing effect Effects 0.000 claims description 13
- 239000011267 electrode slurry Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000004966 Carbon aerogel Substances 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 8
- 150000002642 lithium compounds Chemical class 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 7
- 239000004917 carbon fiber Substances 0.000 claims description 7
- -1 polyethylene Polymers 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
- 239000013543 active substance Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 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
- 239000000126 substance Substances 0.000 claims description 6
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 5
- 229920006037 cross link polymer Polymers 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 230000009471 action Effects 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
- 239000000463 material Substances 0.000 claims description 4
- 238000004806 packaging method and process 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
- 238000004804 winding Methods 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 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
- 229910010699 Li5FeO4 Inorganic materials 0.000 claims description 2
- 229910010648 Li6CoO4 Inorganic materials 0.000 claims description 2
- 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
- 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
- 239000002931 mesocarbon microbead Substances 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 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
- 239000004584 polyacrylic acid Substances 0.000 claims 1
- 230000004913 activation Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract description 2
- 239000007772 electrode material Substances 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
- 210000004027 cell Anatomy 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000009469 supplementation Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000020169 heat generation Effects 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
- 238000010329 laser etching Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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-supplement negative electrode plate lithium ion battery, and relates to the technical field of lithium ion battery electrode materials. According to the invention, the cross-linked high molecular polymer polyvinyl alcohol mixed with the porous carbon material is coated on the negative pole piece of the lithium ion battery, and the lithium supplement agent is filled in the pore diameter of the porous carbon in the cross-linked grid by a coating, magnetron sputtering deposition or spraying coating method, so that accurate and controllable lithium supplement for the negative pole is realized, and the lithium precipitation phenomenon of the negative pole due to transitional lithiation is prevented. On one hand, the selected porous carbon can 'bind' redundant lithium powder in the hole wall, 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 during a certain stage of charging and discharging, along with the increase of the internal temperature of the battery, the activation energy is increased, and the lithium powder bound in the hole diameter is continuously supplemented with lithium. On the other hand, the rich pore diameter 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 lithium ion battery electrode materials, in particular to a preparation method of a porous carbon lithium-supplement negative electrode plate lithium ion battery.
Background
In the first cycle of charging of the lithium ion battery, a solid electrolyte film (SEI film) is formed on the surface of the negative electrode, and about 10% of active lithium in the positive electrode is consumed, resulting in irreversible capacity loss and further reduction of energy density of the lithium ion battery. In order to ensure the capacity of the battery, the lost lithium needs to be supplemented, the technology is pre-lithium, the pre-lithium technology can not only make up the first-effect loss of the anode, but also provide an extra lithium source, and is beneficial to improving the energy density and the cycle performance of the ion battery.
Currently, lithium supplement methods are divided into positive electrode lithium supplement and negative electrode lithium supplement. Among them, the lithium supplement by the negative electrode such as lithium powder and lithium supplement by lithium foil is the most commonly used and the most fundamentally solved problem, and the lithium supplement by the positive electrode can only be increased by orders of magnitude of hundreds of times in the cycle life. However, the process of the negative electrode lithium supplement technology often causes a large amount of heat generation, the process control is difficult, meanwhile, the negative electrode transition lithium supplement is easily generated by adopting the traditional negative electrode hot pressing lithium belt or lithium foil and other modes, and the potential safety hazard is generated by lithium precipitation.
In the prior art, a chinese patent publication No. CN112397682A discloses a negative electrode plate for lithium supplement processing and a lithium ion battery thereof. The negative pole piece that this technical scheme provided effectively improves the pole piece problem of generating heat, and the passageway that lithium supplementation district and clearance district formed can make lithium ion battery annotate the liquid back, and the negative pole piece is infiltrated more effectively to electrolyte, improves battery energy density, can also promote battery cycle life and dynamic properties simultaneously. However, the lithium is supplemented on the surface of the negative electrode layer by intermittent blank leaving, so that the negative electrode layer is distributed at intervals between a lithium supplementing area and a non-lithium supplementing area, and the intermittent control method is complex in process and difficult to apply in a large scale.
The Chinese patent with the publication number of CN112599723A discloses a lithium-supplement negative pole piece, a preparation method thereof and a lithium ion battery. The copper foil is subjected to hole forming in modes of punching, hole pressing, electroplating, corrosion, laser etching and the like, and lithium is supplemented between an upper layer and a lower layer of a copper foil current collector and a negative electrode of the formed hole.
Disclosure of Invention
The invention aims to provide a preparation method of a porous carbon lithium-supplement cathode plate lithium ion battery aiming at the defects of the prior art, which is characterized in that a porous active carbon coating is utilized to supplement lithium in a 'pore bundle' manner, active lithium is uniformly filled into the porous active carbon, uniform and accurate lithium supplement is realized, the cost is low, and the large-scale production is easy.
In order to achieve the above purpose, the invention adopts the technical scheme that:
a preparation method of a porous carbon lithium-supplement negative pole piece lithium ion battery comprises a preparation step of a lithium-supplement negative pole piece, a preparation step of a positive pole piece and a preparation step of a lithium ion battery;
s1 preparation of lithium-supplement negative pole piece
The preparation steps of the lithium supplement negative pole piece comprise negative pole body preparation, porous carbon coating preparation, lithium supplement agent preparation and negative pole piece preparation.
S11, preparing a negative electrode body: mixing and stirring a negative electrode active material, a conductive agent, a first adhesive and a first solvent to obtain negative electrode slurry, adjusting the viscosity of the negative electrode slurry, coating and drying to obtain a negative electrode body.
In the preparation of the negative electrode body, the negative electrode active material comprises one or more of artificial graphite, natural graphite, mesocarbon microbeads, soft carbon and hard carbon.
S12, preparing a porous carbon coating: mixing, stirring 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 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 percent of the porous carbon material is 5-50%. Preferably, the mass percent 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 has rich pore size. 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 and 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, the maximum value of the porous material is reduced to 30-60% on the basis of 30-90%.
In the preparation of the porous carbon coating, the aperture of the porous carbon material is 10-100 nm. Preferably, the pore diameter of the porous carbon material is 50-80 nm.
S13, preparation of a lithium supplement agent: dispersing the simple substance lithium powder or lithium compound and the third adhesive into the third solvent to prepare the lithium supplementing emulsion.
In the preparation of the lithium supplement agent, the mass percentage of the simple substance lithium powder or the lithium compound is 5-90%. Preferably, the mass percentage of the elementary lithium powder or the lithium compound is 20-50%.
In the preparation of the lithium supplement agent, the lithium compound comprises lithium oxide, lithium nitride, lithium sulfide and Li5FeO4、Li6CoO4One or more of lithium hydroxide and lithium carbonate.
In the preparation of the negative electrode body, the preparation of the porous carbon coating and the preparation of the lithium supplement 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 pole piece: and filling and dispersing the lithium supplementing emulsion prepared in the preparation of the lithium supplementing agent into the surface or the aperture of the porous carbon in the cross network on the negative electrode body obtained in the preparation of the porous carbon coating by a coating, magnetron sputtering deposition or spraying coating method to obtain the lithium supplementing negative electrode piece.
In the preparation of the lithium supplement agent, the double-sided spraying thickness of the negative pole piece is 2-4 um.
S2 preparation step of 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 piece.
In the preparation step of the positive pole piece, the positive pole material comprises a positive pole current collector and a positive pole active substance, wherein the positive pole active substance comprises one or more of lithium iron phosphorization, 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, preparation of lithium ion battery
Separating the lithium-supplementing negative pole piece obtained in the step of preparing the lithium-supplementing negative pole piece and the positive pole piece obtained in the step of preparing the positive pole piece by using a diaphragm, winding the positive pole piece and the lithium-supplementing negative pole piece to obtain a naked cell, packaging the naked cell by using a shell, injecting an electrolyte after drying, and obtaining the lithium ion battery through the processes of vacuum packaging, standing, formation and shaping.
In the preparation step of the lithium ion battery, the diaphragm comprises one or more of Polyethylene (PE), polypropylene (PP), polypropylene/polyethylene/polypropylene (PP/PE/PP three-layer composite diaphragm), polytetrafluoroethylene, polyimide and a polyolefin diaphragm coated with ceramic.
The lithium ion battery prepared by the preparation method comprises a positive pole piece, a lithium supplement negative pole piece, a diaphragm for separating the positive pole piece and the lithium supplement negative pole piece, a shell and electrolyte filled in the shell and used for conducting ions between the positive pole piece and the negative pole piece.
The lithium supplement negative pole piece comprises a negative pole body, a porous activated carbon layer which is coated on the surface of the negative pole body and is dispersed by a cross-linked polymer, and a lithium supplement agent which is uniformly filled on the porous activated carbon layer.
The invention has the beneficial effects that:
compared with the prior art, the lithium ion battery negative pole piece is coated with the crosslinked high molecular polymer polyvinyl alcohol mixed with the porous carbon material, and the lithium supplement agent is filled in the pore diameter of the porous carbon in the crosslinked grid by a coating, magnetron sputtering deposition or spraying coating method, so that the accurate and controllable lithium supplement of the negative pole is realized, and the lithium precipitation phenomenon of the negative pole caused by transitional lithiation is prevented. On one hand, the selected porous carbon can 'bind' redundant lithium powder in the hole wall, 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 during a certain stage of charging and discharging, along with the increase of the internal temperature of the battery, the activation energy is increased, and the lithium powder bound in the hole diameter is continuously supplemented with lithium. On the other hand, the rich pore diameter of the porous carbon can also accelerate the infiltration of the 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 surface of the negative electrode is coated with the cross-linked high molecular polymer polyvinyl alcohol mixed with the porous carbon, and then the lithium supplement glue solution is coated, so that the preparation process is simple, and the mass production is easy.
Drawings
FIG. 1 is a schematic diagram showing the distribution of the negative electrode, porous carbon and lithium supplement agent of the battery of the present invention;
FIG. 2 is a comparison of the cycling curves of the cells of the present invention.
Detailed Description
The conception, the specific structure and the technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments and the accompanying drawings to fully understand the objects, the features and the effects of the present invention.
Example 1
A preparation method of a porous carbon lithium-supplement negative pole piece lithium ion battery comprises a lithium-supplement negative pole piece preparation step, a positive pole piece preparation step and a lithium ion battery preparation step.
Preparation of first-stage lithium-supplement negative pole piece
(1) Preparing a negative electrode body: dispersing artificial graphite, acetylene black and PVDF in a solvent NMP according to the weight percentage of 95% to 2.5%, stirring for 4 hours to obtain negative electrode slurry, adjusting the solid content of the negative electrode to be 50%, the viscosity to be 4700 mpa.s and the fineness of the negative electrode slurry to be about 35um, and coating and drying to obtain a negative electrode body.
(2) Preparing a porous carbon coating: mixing, stirring and dispersing the porous activated carbon material according to the mass percentage of 10% of slurry, 20% of cross-linked polymer PVA, 2% of adhesive and NMP solvent according to a certain proportion to prepare porous carbon glue solution, and coating the porous glue solution on the negative electrode body prepared in the step (1).
(3) Preparing a lithium supplement agent: dispersing the simple substance lithium powder into solvent NMP according to the mass percentage of 20% and 3% of adhesive to prepare the lithium-supplementing emulsion.
(4) Preparing a hole beam lithium negative pole piece: and (3) filling the lithium supplement agent coating liquid prepared in the step (3) into the surface or pore diameter of the porous carbon of the negative electrode body in the step (2) by a coating method, wherein the thickness of the double-sided lithium supplement coating is 4 mu m.
Secondly, preparing a positive pole piece
Mixing the positive active substance, 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 a lithium ion battery positive slurry with certain viscosity, uniformly coating the positive slurry on two surfaces of an aluminum foil of a positive current collector, and drying at 85 ℃ to obtain a positive pole piece.
Preparation of lithium ion battery
Separating the 'hole bundle lithium' negative pole piece obtained in the first step and the positive pole piece obtained in the second step by a polyolefin isolating membrane, winding to obtain a naked cell, packaging the naked cell by a shell, injecting electrolyte after drying, and carrying out vacuum packaging, standing, formation, shaping and other procedures to obtain the lithium ion battery.
The lithium ion battery prepared by the preparation method comprises a positive pole piece, a lithium supplement negative pole piece, a diaphragm for separating the positive pole piece and the lithium supplement negative pole piece, a shell and electrolyte filled in the shell and used for conducting ions between the positive pole piece and the negative pole piece.
The lithium supplement negative pole piece comprises a negative pole body, a porous activated carbon layer coated on the surface of the negative pole body and dispersed by a cross-linked polymer, and a lithium supplement agent uniformly filled on the porous activated carbon layer, as shown in figure 1.
Example 2
In the embodiment, the mass ratio of the porous activated carbon in the step (2) in the preparation of the lithium-supplement negative electrode piece in the embodiment 1 is adjusted to be 20% of the porous carbon slurry, the thickness of the double-sided lithium supplement in the step (4) is 3um, and all other steps are the same as the other steps in the embodiment 1.
Example 3
In the embodiment, the mass ratio of the porous activated carbon in the step (2) in the preparation of the lithium-supplement negative electrode piece in the embodiment 1 is adjusted to be 30% of the porous carbon slurry, the thickness of the double-sided lithium supplement in the step (4) is 2um, and all other steps are the same as the other steps in the embodiment 1.
Example 4
In the embodiment, the porous activated carbon in the step (2) in the preparation of the lithium-supplement negative electrode piece in the embodiment 1 is replaced by the porous Carbon Nanotube (CNT), the mass percentage of the porous carbon nanotube is 10% of the porous carbon slurry, the thickness of the double-sided lithium supplement in the step (4) is 4um, and all other steps are the same as the other steps in the embodiment 1.
Example 5
In the embodiment, the porous activated carbon in the step (2) in the preparation of the lithium-supplement negative electrode piece in the embodiment 1 is replaced by the porous Carbon Nanotube (CNT), the mass percentage of the porous carbon nanotube is 20% of the porous carbon slurry, the thickness of the double-sided lithium supplement in the step (4) is 3um, and all other steps are the same as the other steps in the embodiment 1.
Example 6
In the embodiment, the porous activated carbon in the step (2) in the preparation of the lithium-supplementing negative electrode piece in the embodiment 1 is replaced by the porous carbon fiber, the mass percentage of the porous carbon fiber is 10% of the porous carbon slurry, the thickness of the double-sided lithium supplementation in the step (4) is 4um, and all other steps are the same as the other steps in the embodiment 1.
Example 7
In the embodiment, the porous activated carbon in the step (2) in the preparation of the lithium-supplementing negative electrode piece in the embodiment 1 is replaced by the porous carbon fiber, the mass percentage of the porous carbon fiber is 20% of the porous carbon slurry, the thickness of the double-sided lithium supplementation in the step (4) is 3um, and all other steps are the same as the other steps in the embodiment 1.
Example 8
In the embodiment, the porous activated carbon in (2) in the preparation of the lithium-supplementing negative electrode piece in the embodiment 1 is replaced by the porous carbon aerogel, the mass percentage of the porous carbon aerogel is 10% of the porous carbon slurry, the lithium supplementing agent in (3) is lithium powder, the thickness of double-sided lithium supplementation in (4) is 4um, and all other steps are the same as other steps in the embodiment 1.
Example 9
In the embodiment, the porous activated carbon in the step (2) in the preparation of the lithium-supplementing negative electrode piece in the embodiment 1 is replaced by the 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 the step (3) is replaced by the lithium sulfide, the thickness of the double-sided lithium supplementation is 4um, and all other steps are the same as those in the embodiment 1.
Example 10
In the embodiment, the porous activated carbon in the step (2) in the preparation of the lithium-supplement negative electrode piece in the embodiment 1 is replaced by the porous carbon aerogel, the mass percentage of the porous carbon aerogel is 10% of the porous carbon slurry, the lithium supplement agent in the step (3) is replaced by lithium oxide, the thickness of lithium supplement in the double surfaces in the step (4) is 4um, and all other steps are the same as other steps in the embodiment 1.
Example 11
In the embodiment, the porous activated carbon in the step (2) in the preparation of the lithium-supplement negative electrode piece in the embodiment 1 is replaced by the porous carbon aerogel, the mass percentage of the porous carbon aerogel is 10% of the porous carbon slurry, the lithium supplement agent in the step (3) is replaced by the lithium nitride, the thickness of the double-sided lithium supplement in the step (4) is 4um, and all other steps are the same as other steps in the embodiment 1.
Comparative example 1
The first step is as follows: preparation of a hole beam lithium-supplement negative electrode piece:
dispersing artificial graphite, acetylene black and PVDF in a solvent NMP according to the weight percentage of 95% to 2.5%, stirring for 4 hours to obtain negative electrode slurry, and adjusting the solid content of the negative electrode to be 50%, the viscosity to be 4700 mpa.s and the fineness of the negative electrode slurry to be 35 um; dispersing simple substance lithium powder into solvent NMP according to the mass percentage of 20% and 3% of adhesive to prepare lithium-supplementing emulsion; and filling the lithium supplement agent coating liquid on the surface or in the pore diameter of the porous carbon of the negative pole piece by a coating method.
The second step is that: preparation of positive pole piece
Mixing the positive active substance, 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 the positive slurry of the lithium ion battery with certain viscosity, uniformly coating the positive slurry on two surfaces of an aluminum foil of a positive current collector, and drying at 85 ℃ to obtain the positive pole piece.
The third step: preparing a lithium ion battery:
separating the hole beam lithium cathode pole piece in the first step and the positive pole piece in the second step by a polyolefin isolating membrane, winding to obtain a naked cell, packaging the naked cell by a shell, drying, injecting electrolyte, and performing vacuum packaging, standing, formation, shaping and other processes to obtain the lithium ion battery.
Comparative example 2
The first step is as follows: dispersing artificial graphite, acetylene black and PVDF in a solvent NMP according to the weight percentage of 95% to 2.5%, stirring for 4 hours to obtain negative electrode slurry, and adjusting the solid content of the negative electrode to be 50%, the viscosity to be 4700 mpa.s and the fineness of the negative electrode slurry to be 35 um; and coating to obtain the negative pole piece.
The second and third steps were the same as in comparative example 1, and the cells were 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-discharge tests after formation and activation, and lithium supplement parameters and cell performance data are shown in table 1 below.
TABLE 1 Pole piece lithium supplement parameters and corresponding Battery electrochemical Performance
The test results in table 1 show that, compared with comparative example 2, the first coulombic efficiency of the lithium-supplement negative electrode plate is obviously superior to that of the lithium-supplement negative electrode plate which is not supplemented, mainly because the lithium-supplement layers on the inner and outer surfaces of the porous carbon supplement lithium ions Li + consumed in the SEI film formation process, and in addition, along with the increase of the cycle times, the cycle capacity retention rate of the battery for 1000 times is greatly improved compared with that of the battery which is not supplemented with the lithium negative electrode material, so that the lithium-supplement agent bound in the pore diameter of the porous carbon material continuously outputs the lithium-supplement agent to supplement the lithium ions in the positive electrode material, the consumption of the lithium ions in the positive electrode is reduced, the positive electrode material is efficiently utilized, and the service life of the battery is prolonged.
In addition, as can be seen from the comparison of examples 1 to 11, the porous carbon, the carbon nanotube, the carbon aerogel and the carbon fiber have no great difference in performance, the porous activated carbon is economical to select in view of cost, and on the other hand, the lithium powder is the best lithium supplement agent relative to the lithium compound in view of safety in comparison of the lithium supplement agent.
Compared example 1 and example 2 can see that, there is not porous carbon glue layer to do "hole beam lithium" effect between negative pole layer and lithium supplement layer, and the battery performance difference is great, has "hole beam lithium" carbon layer can accurate control the volume of lithium, can control the speed of supplementing lithium again, prevents local overheat, and the intensification is too fast, and rich lithium is appeared and is educed the lithium phenomenon, and then the dendrite pierces through the diaphragm, produces the potential safety hazard.
The battery cycling curves of examples 1, 5 and 2 are compared as shown in fig. 2, wherein in fig. 2, the a curve is the change of the battery capacity of example 1 with the increase of the cycle number, the b curve is the change of the battery capacity of example 5 with the increase of the cycle number, and the c curve is the change 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 batteries of examples 1 and 5 of the invention are better than the battery capacity of comparative example 2 with the increase of the cycle number.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and those skilled in the art can make various equivalent modifications or substitutions without departing from the spirit of the present invention, and the equivalents or substitutions are included in the scope of the present invention defined by the claims.
Claims (10)
1. A preparation method of a porous carbon lithium-supplement cathode plate lithium ion battery is characterized by comprising the following steps: the method comprises the steps of preparing a lithium-supplement negative pole piece, preparing a positive pole piece and preparing a lithium ion battery;
the preparation method of the lithium-supplement negative pole piece comprises the following steps:
preparing a negative electrode body: mixing and stirring a negative electrode active material, a conductive agent, a first adhesive and a first solvent to obtain negative electrode slurry, adjusting the viscosity of the negative electrode slurry, coating and drying to obtain a negative electrode body;
preparing a porous carbon coating: mixing, stirring 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 obtained in the preparation of the negative electrode body to obtain a negative electrode body containing porous carbon;
preparing a lithium supplement agent: dispersing simple substance lithium powder or a lithium compound and a third adhesive into a third solvent to prepare a lithium supplementing emulsion;
preparing a negative pole piece: 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 an interconnection network on a negative electrode body obtained in the preparation of the porous carbon coating by a coating, magnetron sputtering deposition or spraying coating method to obtain a lithium supplementing negative electrode piece;
the preparation method comprises the steps of preparing a positive pole piece, mixing a positive pole material, a second conductive agent and a fourth adhesive, stirring and homogenizing under the action of a vacuum stirrer to obtain a lithium ion battery positive pole slurry with certain viscosity, uniformly coating the positive pole slurry on two surfaces of an aluminum foil of a positive pole current collector, and drying to obtain the positive pole piece;
the preparation method comprises the steps of preparing a lithium ion battery, namely separating the lithium supplement negative pole piece obtained in the preparation step of the lithium supplement negative pole piece and the positive pole piece obtained in the preparation step of the positive pole piece by using a diaphragm, winding the positive pole piece and the lithium supplement negative pole piece to obtain a naked battery cell, packaging the naked battery cell by using a shell, injecting electrolyte after drying, and carrying out vacuum packaging, standing, formation and shaping procedures to obtain the lithium ion battery.
2. The method of claim 1, wherein: in the preparation of the negative electrode body, the negative electrode active material comprises one or more of artificial graphite, natural graphite, mesocarbon microbeads, soft carbon and hard carbon.
3. The method of 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 of claim 1, wherein: in the preparation of the porous carbon coating, the mass percent of the porous carbon material is 5-50%, the porosity is 30-90%, and the pore diameter is 10-100 nm.
5. The method of claim 1, wherein: in the preparation of the lithium supplement agent, the mass percentage of the simple substance lithium powder or the lithium compound is 5-90%.
6. The method of claim 1, wherein: in the preparation of the lithium supplement agent, the lithium compound comprises lithium oxide, lithium nitride, lithium sulfide and Li5FeO4、Li6CoO4One or more of lithium hydroxide and lithium carbonate.
7. The method of claim 1, wherein: in the preparation of the negative electrode body, the preparation of the porous carbon coating and the preparation of the lithium supplement 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-methyl pyrrolidone.
8. The method of claim 1, wherein: in the preparation of the lithium supplement agent, the double-sided spraying thickness of the negative pole piece is 2-4 um.
9. The method of claim 1, wherein: in the preparation step of the positive pole piece, the positive pole material comprises a positive pole current collector and a positive pole active substance, wherein the positive pole active substance comprises one or more of lithium iron phosphorization, 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.
10. The method of claim 1, wherein: in the preparation step of the lithium ion battery, the diaphragm comprises one or more of polyethylene, polypropylene/polyethylene/polypropylene three-layer composite diaphragm, polytetrafluoroethylene, polyimide and polyolefin diaphragm coated with ceramic.
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