CN115036444A - Pre-lithiation and pre-sodium-treatment composite negative electrode material and preparation method and application thereof - Google Patents
Pre-lithiation and pre-sodium-treatment composite negative electrode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN115036444A CN115036444A CN202110234014.XA CN202110234014A CN115036444A CN 115036444 A CN115036444 A CN 115036444A CN 202110234014 A CN202110234014 A CN 202110234014A CN 115036444 A CN115036444 A CN 115036444A
- Authority
- CN
- China
- Prior art keywords
- sodium
- lithium
- sheet
- negative electrode
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 76
- 239000011734 sodium Substances 0.000 title claims abstract description 76
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000006138 lithiation reaction Methods 0.000 title claims description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 70
- 239000011888 foil Substances 0.000 claims abstract description 64
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000010405 anode material Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 24
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 18
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- 239000011889 copper foil Substances 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- 238000005096 rolling process Methods 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 239000011149 active material Substances 0.000 claims description 8
- 239000006258 conductive agent Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- 229910052582 BN Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- -1 Polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000003273 ketjen black Substances 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000006245 Carbon black Super-P Substances 0.000 claims description 3
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 2
- 229910010941 LiFSI Inorganic materials 0.000 claims description 2
- 229910021201 NaFSI Inorganic materials 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920001289 polyvinyl ether Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 17
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 11
- 230000007847 structural defect Effects 0.000 abstract description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000011267 electrode slurry Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical group FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a pre-lithium and pre-sodium composite negative electrode material and a preparation method and application thereof, relating to the preparation of lithium ion or sodium ion half batteries and full batteries and the improvement of electrochemical performance thereof, wherein a negative electrode plate is directly contacted with a lithium foil or a sodium foil under the soaking of electrolyte so as to pre-enter lithium and sodium ions into the surface and the internal structure of the composite material of the negative electrode plate, construct an SEI film on the surface of the negative electrode plate and fill the structural defects of the composite material; meanwhile, the coulombic efficiency range of the first circle of the composite material is adjusted by controlling the conditions of the short-circuit pressure, the time, the voltage and the like in the processes of pre-lithium treatment and pre-sodium treatment, the composite material meets the matching requirement of the full-battery anode material, and the cycle performance and the rate performance of the full-battery are kept.
Description
Technical Field
The invention belongs to the technical field of batteries, relates to a pre-lithiation and pre-sodium-treatment composite negative electrode material, and a preparation method and application thereof, and particularly relates to a composite negative electrode material for controllably improving the first-turn coulombic efficiency of a two-dimensional composite material of a lithium-ion battery and a sodium-ion battery, and a preparation method and application thereof.
Background
The two-dimensional composite negative electrode material provides a large number of active points for the rapid storage of the pseudocapacitance property of lithium ions due to the unique two-phase interface, so that the two-dimensional composite negative electrode material has higher reversible capacity (500 mAh/g) than the existing commercialized graphite negative electrode, and thus shows excellent rate performance and cycling stability. However, the large specific surface area of the two-dimensional composite material can form a large area of solid electrolyte interface film (SEI film) on the surface of the composite material particles during the first charge and discharge process of the material, thereby preventing the reversible adsorption and desorption of lithium ions; on the other hand, structural defects existing on the surface of the two-dimensional composite material also serve as partial lithium ion 'traps', so that lithium ions entering the 'traps' cannot be charged and discharged reversibly. Based on the structural defects, the first-turn coulombic efficiency of the two-dimensional composite material is low (50-60%), and great difficulty is caused to the practicability of the two-dimensional composite material.
At present, a commonly used method for improving the first-turn coulombic efficiency of a two-dimensional composite material comprises the following steps: (1) the surface of the material is coated with a carbon or metal oxide layer to reduce the chemical structure defects on the surface of the material, thereby reducing the probability of lithium ions entering a 'trap'. However, neither dry coating nor wet coating can stably control the uniformity and integrity of the coating layer; and if the coating layer is too thick, the battery impedance is increased, and the battery capacity is reduced; in addition, the coating process further increases the production cost of the material. (2) A small amount of film-forming additive is added into the electrolyte, and the film-forming additive can be reduced on the surface of the negative electrode material to form a stable SEI film in preference to solvents such as EC and DEC during battery discharge, so that the quantity of lithium ions entering the SEI film in the material is reduced, and the adsorption and desorption reversibility of the lithium ions is improved. The method is simple to operate, and can solve the technical problem that the first-turn coulombic efficiency of the conventional graphite negative electrode material is low, but for the two-dimensional composite material with low first-turn coulombic efficiency, the method still has difficulty in enabling the first-turn coulombic efficiency to reach the commercialization level; (3) by a negative electrode lithium supplement technology: for example, lithium powder can be added in the negative electrode slurry mixing process or directly sprayed on the surface of the negative electrode pole piece to additionally provide a part of lithium ions in the first charging process, so that the first-turn coulombic efficiency of the negative electrode material is improved. However, the method is complicated to operate and has high requirements on environment and equipment. Therefore, how to simply, rapidly and controllably improve the first-turn coulombic efficiency of the material so as to improve the first-turn coulombic efficiency of lithium, sodium half-cells and full-cells becomes a technical problem to be solved urgently.
Disclosure of Invention
In order to improve the technical problem, the invention provides a preparation method of a pre-lithiation and pre-sodium-treatment composite negative electrode material, which comprises the steps of attaching a lithium sheet and/or a sodium sheet to a battery negative electrode sheet, adding an electrolyte, and pressing to obtain the pre-lithiation and/or pre-sodium-treatment composite negative electrode material.
According to an embodiment of the present invention, the negative electrode sheet is a sheet-shaped battery negative electrode sheet. Preferably, the thickness of the sheet-shaped battery negative pole piece is 5-20 μm, and is exemplified by 5 μm, 10 μm, 15 μm and 20 μm.
According to the embodiment of the invention, the current collector of the sheet-shaped battery negative pole piece is a metal foil made of pure metal foil or alloy material. Preferably a pure metal foil. For example, the pure metal foil is a copper foil or an aluminum foil.
According to the embodiment of the invention, the active material of the sheet-shaped battery negative pole piece is a two-dimensional material. For example, the two-dimensional material may be selected from TiO 2 、MnO 2 、RuO 2 、V 2 O 5 、MoO 3 、MoS 2 、WS 2 、La 2 TiO 3 、LaNb 2 O 7 、Ca 2 Nb 3 O 10 Graphene, C 3 N 4 One, two or more of (graphite carbon nitride), BN (boron nitride), Mxene (transition metal carbonitride), and LDHs (layered double hydroxide). Preferably two. For example, the two-dimensional material may be selected from TiO 2 And graphene composite materials.
According to the embodiment of the invention, the sheet-shaped battery negative electrode plate further contains a conductive agent and/or a binder.
According to an embodiment of the present invention, the conductive agent is at least one of conductive carbon Black, acetylene Black, carbon Black (Super-P), ketjen Black (KT-Black) conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene, and reduced graphene oxide.
According to an embodiment of the present invention, the binder is selected from at least one of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), Styrene Butadiene Rubber (SBR), sodium alginate, copolymers of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polyhexafluoropropylene, and the like.
According to the embodiment of the invention, the mixing mass ratio of the active material, the conductive agent and the adhesive of the sheet-shaped battery negative pole piece is (6-9.8): (0.1-3): 0.1-2); preferably (8-9), (0.5-1); exemplary are 6:2:2, 7:1.5:1.5, 8:1:1, 9:0.5:0.5, 9.8:0.1: 0.1.
According to the embodiment of the invention, the preparation method of the sheet-shaped battery negative pole piece comprises the following steps:
mixing an active material of the battery negative pole piece with a conductive agent and a binder, then adding a solvent for dispersion to obtain negative pole slurry, coating the negative pole slurry on a negative pole current collector, drying, rolling and die-cutting to obtain the flaky battery negative pole piece.
According to the embodiment of the invention, in the preparation method of the sheet-shaped battery negative pole piece, the rolling pressure is 0-20 MPa, and the rolling time is 0-120 s.
According to the embodiment of the invention, the drying is preferably vacuum drying. Preferably, the drying temperature is 60 to 110 ℃, preferably 70 to 100 ℃, and exemplarily 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃. Further, the drying time is 0.5-20 h, preferably 12-20 h, and examples are 12h, 14h, 16h, 18h and 20 h.
According to the embodiment of the invention, the battery negative pole piece is rolled and sliced to be made into a pole piece with the size required by a button or soft package battery.
According to the embodiment of the invention, before the lithium sheet and/or the sodium sheet is attached to the battery negative pole piece, the lithium sheet and/or the sodium sheet is rolled into a lithium foil or a sodium foil with a smooth surface and a thickness of less than or equal to 200 mu m. Preferably, under the protection of inert atmosphere, the lithium sheet and/or the sodium sheet are rolled into lithium foil or sodium foil with smooth surface and thickness less than or equal to 200 mu m. More preferably, the inert atmosphere is a nitrogen or argon atmosphere. For example, in a glove box under an argon atmosphere. Further, the area of the rolled lithium sheet and/or sodium sheet is larger than that of the negative pole piece, so that the lithium sheet and/or sodium sheet can cover the whole negative pole piece.
According to the embodiment of the invention, the dosage of the electrolyte is 20-400 mu L/cm 2 Exemplary is 20. mu.L/cm 2 、50μL/cm 2 、80μL/cm 2 、100μL/cm 2 、150μL/cm 2 、200μL/cm 2 、250μL/cm 2 、300μL/cm 2 、350μL/cm 2 、400μL/cm 2 。
According to an embodiment of the present invention, the solute of the electrolyte is a lithium salt or a sodium salt.
For example, the lithium salt includes LiPF 6 、LiTFSI、LiBOB、LiClO 4 、LiFSI、LiBF 4 And LiAsF 6 At least one of; preferably LiPF 6 。
For example, the sodium salt comprises NaPF 6 ，NaClO 4 At least one of NaTFSI and NaFSI; preferably NaClO 4 。
According to an exemplary embodiment of the present invention, the concentration of the lithium salt and the sodium salt is 1M.
According to an embodiment of the present invention, the solvent of the electrolyte includes two or three of Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DEC), diethyl carbonate (DMC), methyl ethyl carbonate (EMC), and the like. For example, when two or three of the above solvents are selected, the volume ratio thereof may be 1:1 or 1:1: 1.
According to the embodiment of the invention, the smooth side of the lithium foil and/or the sodium foil is preferably faced to the negative pole piece, and the lithium foil and/or the sodium foil completely covers and clings to the negative pole piece. Preferably, the attaching step is performed under protection of an inert atmosphere. More preferably, the inert atmosphere is a nitrogen or argon atmosphere. For example, in a glove box under an argon atmosphere.
According to an embodiment of the invention, the pressing pressure is 0 to 2MPa, preferably 0.1 to 1MPa, exemplary 0.1MPa, 0.15MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.8MPa, 1.0MPa, 2 MPa.
According to an embodiment of the invention, the pressing is allowed to stand for 0-120 min, preferably 2-60 min, exemplary 2min, 5min, 10min, 12min, 15min, 20min, 30min, 60min, 90 min.
Wherein: time is counted from the start of the application of pressure. In the standing process, because of potential difference, the battery is equivalent to a self-discharge process, and lithium ions and sodium ions in the lithium foil and/or the sodium foil enter the surface and the internal structure of an active material of the negative pole piece through electrolyte.
Further, in the direct short circuit state, lithium ions and/or sodium ions in the lithium foil and/or the sodium foil are continuously inserted into the surface and the inside of the active material in the negative electrode pole piece, and the speed of the lithium ions and/or the sodium ions entering the negative electrode pole piece is related to the magnitude of the applied pressure. In the process of pre-lithiation and/or pre-sodium treatment in a short-circuit state, on one hand, a part of artificial SEI film is generated on the surface of the material in advance so as to reduce the consumption of lithium ions and/or sodium ions in the counter electrode in the subsequent first-circle discharging process; on the other hand, the defects in the two-dimensional material are filled with lithium ions and/or sodium ions, so that the surface of the two-dimensional material can be filled with traps which can not reversibly desorb or absorb lithium ions and sodium ions, and the reversible charge-discharge capacity of the two-dimensional material can be improved.
According to the embodiment of the invention, after the pre-lithiation and/or pre-sodium treatment, the voltage of the battery formed by the lithium foil and/or the sodium foil and the negative electrode plate is 1-2V, preferably 1.2-1.7V, and is exemplified by 1V, 1.27V, 1.35V, 1.45V, 1.5V, 1.6V, 1.64V, 1.7V, 1.8V, 1.9V and 2.0V. The voltage of the primary battery after pre-lithiation and/or pre-sodium treatment is controlled within the range of 1-2V, so that the first-turn charging and discharging efficiency of the two-dimensional composite material can be improved to 80-100%.
During the pre-lithiation and/or pre-sodium treatment, the anode (lithium foil and/or sodium foil) and the cathode are connected with a universal meter to detect the voltage change condition at two ends of the battery by separating the two short-circuited poles (lithium foil and/or sodium foil and cathode pole piece) or adding a diaphragm between the two poles, the battery voltage and the quantity and degree of lithium and sodium ions inserted into the pre-lithiation and/or pre-sodium treatment are in linear relation, and the pre-lithiation and/or pre-sodium treatment degree can be controlled according to the voltage change condition.
According to an embodiment of the invention, the preparation method further comprises a step of separating the pressed lithium foil and/or sodium foil from the negative electrode plate, or adding a separator between the lithium foil and/or sodium foil and the negative electrode plate.
According to the embodiment of the invention, the preparation method further comprises the step of airing or washing the separated negative pole piece so as to remove the electrolyte left on the surface of the negative pole piece. Preferably, the washing solvent may be DMC.
According to the embodiment of the invention, the electrolyte on the surface of the lithium foil and/or the sodium foil can be reused after being sucked dry.
According to the embodiment of the invention, the preparation method further comprises the step of drying the washed negative pole piece. For example, the drying may be air drying.
The invention also provides the composite negative electrode material prepared by the preparation method and subjected to pre-lithiation and pre-sodium treatment. Preferably, the composite anode material is a two-dimensional composite anode material.
The invention also provides application of the composite negative electrode material subjected to pre-lithiation and pre-sodium treatment in a lithium battery. Preferably as an application in a negative electrode of a lithium battery.
The invention also provides a lithium battery or a sodium battery, which contains the composite negative electrode material and/or the negative electrode pole piece after pre-lithiation and pre-sodium treatment. Preferably, the lithium battery or the sodium battery may be a half battery or a full battery. For example, the half-cell may be a 2032 button half-cell.
According to an embodiment of the invention, the half-cell further comprises a lithium and/or sodium sheet.
According to an embodiment of the invention, the half cell further comprises a separator. Preferably, the separator may be at least one of PP, PE, PP/PE/PP, glass fiber, and the like. More preferably, the separator is a single-sided and/or double-sided ceramic-coated separator. For example, the charge-discharge interval of the separator is 0.005 to 3V.
According to an embodiment of the present invention, the full cell further includes a positive electrode tab. Preferably, the positive electrode material of the positive electrode plate includes at least one of ternary positive electrode materials such as lithium cobaltate, lithium iron phosphate, sodium vanadium phosphate, cobalt nickel manganese and the like.
Preferably, the capacity ratio of the negative electrode to the positive electrode is 1.0-1.2, exemplary is 1.0, 1.10, 1.2, and preferably is 1.10.
The invention can match the specific capacity of the cathode after pre-lithiation and pre-sodium modification according to the requirement of the first-circle discharge capacity of the pre-lithiation and pre-sodium modification semi-battery; and the charging and discharging interval of the full battery can refer to the charging and discharging interval range commonly used by the anode material.
According to an embodiment of the present invention, the full cell further includes an electrolyte and a separator.
According to an embodiment of the present invention, the electrolyte may be a conventional electrolyte known in the art for lithium and/or sodium batteries, preferably 1M LiPF 6 + EC/DEC (lithium cell) 1:1, 1M NaClO 4 + EC/PC (sodium battery) at a 1:1 volume ratio.
According to an embodiment of the present invention, the separator may be selected from commercially available separators known in the art, preferably Celgard 2500.
The invention has the beneficial effects that:
(1) according to the invention, the pre-lithiation or pre-sodium treatment is carried out on the two-dimensional composite negative electrode material, so that the first-turn charging and discharging efficiency of the half-cell assembled by the two-dimensional composite negative electrode material after the pre-lithiation or pre-sodium treatment can be improved to 80-100% (while the first-turn charging and discharging efficiency of the half-cell assembled by the two-dimensional composite negative electrode material without pre-lithiation or pre-sodium treatment is 50-60%); and the first-turn charge and discharge efficiency of the full battery formed by assembling the two-dimensional composite negative electrode materials subjected to pre-lithiation or pre-sodium treatment can reach the first-turn charge and discharge efficiency equivalent to that of the commercialized negative electrode materials such as graphite. Meanwhile, after the pre-lithiation or pre-sodium treatment two-dimensional composite negative electrode material is assembled into a full battery, the capacity of the positive electrode material can be fully exerted (the capacity of the positive electrode material can be wasted by more than 40% due to the non-pre-lithiation or non-pre-sodium treatment two-dimensional composite negative electrode material), and compared with negative electrode materials such as graphite (the theoretical capacity is 372mAh/g), the weight of the negative electrode adopted by the invention can be reduced by 40-50%, so that the energy density of the full battery can be obviously improved.
(2) Compared with lithium supplement processes such as adding lithium powder into materials or pole pieces, the process route is complex, large-scale equipment such as a spraying device and the like needs to be added, the operation is complex, simple substance lithium can only be added on the surface layer of the materials and cannot enter the interior of material particles, and therefore the first-effect further promotion is limited. The method has the advantages that the process route is simple to operate, the process amplification is convenient, the continuous production can be carried out, the supplemented lithium ions or sodium ions can enter the internal structure of the material, the first effect can be improved by nearly or more than 100%, the lithium foil or the sodium foil can be repeatedly used, and the production cost is low.
(3) The two-dimensional material is pre-lithiated or pre-sodiumized by adopting a positive and negative short circuit contact mode, the pressure of the pre-lithiation process is increased, the rapid pre-lithiation or pre-sodiumizing process can be carried out, the total time is controlled within 5-15 min, and the production efficiency and the productivity are greatly improved.
(4) Through the pressure control of the short-circuit pre-lithium process and the voltage control of the half cell, the stability and the repeatability of the process are improved, and through the stable control of the cut-off voltage, the first-turn efficiency and the consistency of discharge capacity of different batches are improved, and the actual production requirements are met.
(5) After the negative pole piece treated by the lithium or sodium pre-treatment process forms a half-cell or a full-cell, the cycle performance and the rate performance are kept, and no side effect is generated on the electrochemical performance of the two-dimensional composite material.
(6) The first-effect and first-loop discharge capacities are conveniently adjusted through lithium or sodium pre-treatment time, pressure and voltage control, so that the first-effect and first-loop discharge capacities are adapted and matched with different first-effect anode materials to form the full battery, the capacities of the anode materials and the cathode materials are fully exerted, and the energy density of the full battery is further improved.
Drawings
Fig. 1 is a first-turn charge-discharge curve diagram of a half-cell assembled by the pre-lithiated two-dimensional composite anode material in example 1.
Fig. 2 is a first-turn charge-discharge curve diagram of a full battery assembled by the two-dimensional composite anode material before and after pre-lithiation in example 2.
Fig. 3 is a graph of the cycle performance of a full cell assembled from two-dimensional composite anode materials before and after prelithiation in example 2.
Fig. 4 is a rate performance graph of a full cell assembled by the two-dimensional composite anode material before and after prelithiation in example 2.
Fig. 5 is a first-turn charge and discharge curve diagram of a full cell assembled by the pre-lithiated two-dimensional composite anode material of example 4.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the techniques realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
In the following examples of the present invention, the two-dimensional material used was TiO 2 And graphene composite (TiO) 2 The preparation method thereof can be found in the method disclosed in patent application example 2 with publication number CN 112125334A.
Example 1
(1) According to the mass ratio of TiO 2 Weighing raw materials according to proportion of carbon black (Super-P) and PVDF (polyvinylidene fluoride) in proportion of 8:1:1, adding NMP (N-methyl pyrrolidone) solvent to prepare negative electrode slurry with solid content of 40%, and then preparing the slurry according to proportion of 2mg/cm 2 Uniformly coating the conductive copper foil with the thickness of 9 mu m on the conductive copper foil with the dosage of the conductive copper foil to form a negative pole piece with the coating thickness of 100 mu m, rolling the negative pole piece under the pressure of 20MPa and drying the negative pole piece in vacuum at the temperature of 100 ℃, and cutting the negative pole piece into a pole piece with the diameter of 10 mm;
(2) the surface of the pole piece prepared in the step (1) is 100 mu L/cm 2 Dropping electrolyte (1M LiPF) 6 EC/DEC in a volume ratio of 1: 1) to wet the pole piece, and then a lithium foil (from multireagent) rolled to a thickness of 150 μm with a stainless steel stick was laminated to the surface of the pole piece (wherein: the lithium foil and the pole piece are completely attached), the pressure is 0.2MPa, the time is 5min, and the open-circuit voltage is detected to be 1.6V after completion;
(3) separating the lithium foil from the pole piece, washing residual electrolyte on the surface of the pole piece by using a solvent DMC, and then airing the pole piece;
(4) assembling the pole pieces prepared in the step (3) into 2032 button half-cells, wherein the diaphragm is Celgard2500 (purchased from multi-reagent), the counter electrode is a lithium piece, and the electrolyte is 1M LiPF 6 EC/DEC in a volume ratio of 1: 1.
The half cell assembled in this example was charged and discharged at 130mA/g, and the result is shown in FIG. 1. As can be seen from the figure: the charge-discharge interval of a half-cell assembled by the pre-lithiated two-dimensional composite negative electrode material is 0.005-3V, the discharge capacity of the first circle is 712mAh/g, and the charge-discharge efficiency of the first circle is 102%.
Example 2
(1) According to the weight ratio of TiO 2 The raw materials are weighed according to the ratio of KT-black PVDF (KT-black) 9:0.5:0.5, NMP solvent is added to prepare negative electrode slurry with the solid content of 35%, and then the slurry is prepared according to the ratio of 3mg/cm 2 Uniformly coating the conductive copper foil with the thickness of 9 mu m with the amount of the conductive copper foil to form a negative pole piece with the coating thickness of 200 mu m, rolling the negative pole piece under the pressure of 15MPa, drying the negative pole piece in vacuum at the temperature of 110 ℃, and cutting the negative pole piece into a pole piece with the diameter of 12 mm;
(2) the surface of the pole piece prepared in the step (1) is 500 mu L/cm 2 Dropping electrolyte (1M LiPF) 6 EC/D of 1:1 by volumeEC) to wet the pole piece, then roll it to a lithium foil (from multireagent) with a thickness of 100 μm with a stainless steel pin and press it all onto the pole piece surface (where: the lithium foil is completely attached to the pole piece), the pressure is 0.1MPa, the time is 12min, and the open-circuit voltage is detected to be 1.45V after completion;
(3) separating the lithium foil from the pole piece, washing residual electrolyte on the surface of the pole piece by using a solvent DMC, and then airing the pole piece;
(4) assembling the pole pieces prepared in the step (3) into a 2032 button type full cell: lithium iron phosphate (LiFePO) is used as the anode of the full cell 4 ) The negative electrode/positive electrode capacity N/P is 1.10, the diaphragm is an alumina ceramic double-sided coating PP diaphragm (purchased from a star source material, the thickness of the PP coating layer is 4 mu M), and the electrolyte is 1M LiPF 6 EC/DEC in a volume ratio of 1: 1.
The full cell assembled in this example was subjected to charge and discharge tests, and the results are shown in fig. 2. As can be seen from the figure: the charge-discharge interval of the full battery assembled by the pre-lithiated two-dimensional composite negative electrode material is 1-3.7V, the current is 0.1C (17mA/g), the coulombic efficiency of the first circle is 81.7%, and the discharge capacity is 145.4 mAh/g. The discharge capacity after 30 cycles of circulation is 144.8mAh/g, the capacity retention rate is 99 percent,
by way of comparison, LiFePO without lithiation 4 -TiO 2 The result of charging and discharging the/C full cell is shown in FIG. 3. As can be seen from the figure: the first-circle discharge capacity of the full battery assembled by the unlithiated two-dimensional composite negative electrode material is only 97.1mAh/g, the first-circle charge-discharge efficiency is only 57.8%, and the discharge capacity after 27 circles of circulation is only 55.9 mAh/g. Therefore, the capacity of the anode material can be fully exerted after the full cell is assembled by the pre-lithiation or pre-sodium treatment two-dimensional composite anode material, so that the authorized coulombic efficiency and the cycle performance of the full cell are obviously improved.
Example 3
(1) According to the weight ratio of TiO 2 Weighing raw materials of KT-black (PVDF) 8:1:1, adding NMP solvent to prepare negative electrode slurry with the solid content of 32%, and then preparing the slurry according to the proportion of 1mg/cm 2 In an amount to be uniformly coated on a conductive copper foil having a thickness of 9 μm to form a coating thicknessAfter the negative pole piece with the temperature of 80 mu m is rolled under 12MPa and dried in vacuum at 90 ℃, the negative pole piece is cut into pole pieces with the diameter of 14 mm;
(2) the surface of the pole piece prepared in the step (1) is 400 mu L/cm 2 Dropping electrolyte (1M LiPF) 6 EC/DEC in a volume ratio of 1: 1) to wet the pole piece, then a stainless steel stick was rolled to a lithium foil (from multireagent) with a thickness of 120 μm and pressed all over the pole piece surface (where: the lithium foil is completely attached to the pole piece), the pressure is 0.3MPa, the time is 20min, and the open-circuit voltage is detected to be 1.64V after completion;
(3) separating the lithium foil from the pole piece, and airing the residual electrolyte on the surface of the pole piece;
(4) assembling the pole pieces prepared in the step (3) into a 2032 button type full cell: lithium cobaltate is used as the positive electrode of the full-cell, the capacity N/P of the negative electrode/the positive electrode is 1.10, the diaphragm is an alumina ceramic double-sided coating PP diaphragm (purchased from a star source material, the thickness of the PP coating layer is 4 mu M), and the electrolyte is 1M LiPF 6 EC/DEC in a volume ratio of 1: 1.
The full cell assembled in this example was subjected to charge and discharge tests, and the results are shown in fig. 4. As can be seen from the figure: the charge-discharge interval of the full battery assembled by the pre-lithiated two-dimensional composite negative electrode material is 0.005-4.4V (0.1C becomes 0.005-4.2V), the current is 0.1C (18mA/g), the coulombic efficiency of the first circle is 93.4%, the discharge capacity is 159.6mAh/g, the 0.2C (36mA/g) discharge capacity is 167.7mAh/g, the 0.5C (90mA/g) discharge capacity is 141.4mAh/g, the 1C (180mA/g) discharge capacity is 119.8mAh/g, the 2C (360mA/g) discharge capacity is 98.6mAh/g, and the 5C (900mA/g) discharge capacity is 71.6 h/g.
Example 4
(1) According to the weight ratio of TiO 2 Weighing raw materials of KT-black (PVDF) 8:1:1, adding NMP solvent to prepare negative electrode slurry with solid content of 35%, and then preparing the slurry according to the proportion of 2mg/cm 2 Uniformly coating the conductive copper foil with the thickness of 9 mu m on the conductive copper foil to form a negative pole piece with the coating thickness of 100 mu m, rolling the negative pole piece under the pressure of 15MPa, drying the negative pole piece in vacuum at the temperature of 90 ℃, and cutting the negative pole piece into a pole piece with the diameter of 10 mm;
(2) the surface of the pole piece prepared in the step (1) is according to300μL/cm 2 Electrolyte (1M NaClO) was added dropwise 4 EC + PC + 5% by volume FEC at a volume ratio of 1: 1) to wet the pole pieces, and then a sodium foil rolled to a thickness of 200 μm with a stainless steel pin was laminated on the surface of the pole pieces (wherein: the lithium foil is completely attached to the pole piece), the pressure is 0.15MPa, the time is 30min, and the open-circuit voltage is detected to be 1.27V after completion;
(3) separating the sodium foil from the pole piece, washing the residual electrolyte on the surface of the pole piece by using a solvent DMC, and then airing the pole piece;
(4) assembling the pole pieces prepared in the step (3) into a 2032 button type full cell: the positive electrode of the full cell uses sodium vanadium phosphate, the negative electrode/positive electrode capacity N/P is 1.05, the diaphragm is Whatman glass fiber (from multi-reagent), the electrolyte is 1M NaClO 4 EC + PC + 5% volume FEC in a volume ratio of 1: 1.
The full battery assembled in this example was subjected to a charge and discharge test, and the results are shown in fig. 5. As can be seen from the figure: the charge-discharge interval of the full battery assembled by the pre-sodium-treated two-dimensional composite negative electrode material is 2-4.2V, the current is 0.1C (20mA/g), the coulombic efficiency of the first circle is 95.4%, and the discharge capacity is 145.4 mAh/g.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a pre-lithiation and pre-sodium-treatment composite negative electrode material is characterized by comprising the steps of attaching a lithium sheet and/or a sodium sheet to a battery negative electrode sheet, adding an electrolyte, and pressing to obtain the pre-lithiation and/or pre-sodium-treatment composite negative electrode material.
Preferably, the negative electrode plate is a sheet-shaped battery negative electrode plate. Preferably, the thickness of the sheet-shaped battery negative pole piece is 5-20 μm.
Preferably, the current collector of the sheet-shaped battery negative electrode piece is a metal foil made of pure metal foil or alloy material. Preferably a pure metal foil. For example, the pure metal foil is a copper foil or an aluminum foil.
2. The method according to claim 1, wherein the active material of the sheet-like battery negative electrode sheet is a two-dimensional material.
Preferably, the two-dimensional material is selected from TiO 2 、MnO 2 、RuO 2 、V 2 O 5 、MoO 3 、MoS 2 、WS 2 、La 2 TiO 3 、LaNb 2 O 7 、Ca 2 Nb 3 O 10 Graphene, C 3 N 4 One, two or more of (graphite carbon nitride), BN (boron nitride), Mxene (transition metal carbonitride), and LDHs (layered double hydroxide). Preferably two. For example, the two-dimensional material may be selected from TiO 2 And graphene composite materials.
3. The production method according to claim 1 or 2, wherein the sheet-like battery negative electrode sheet further contains a conductive agent and/or a binder.
Preferably, the conductive agent is at least one of conductive carbon Black, acetylene Black, carbon Black (Super-P), ketjen Black (KT-Black) conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene and reduced graphene oxide.
Preferably, the binder is at least one selected from polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), Styrene Butadiene Rubber (SBR), sodium alginate, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polyhexafluoropropylene, and the like.
Preferably, the mixing mass ratio of the active material, the conductive agent and the adhesive of the sheet-shaped battery negative pole piece is (6-9.8): (0.1-3): 0.1-2); preferably (8-9), (0.5-1).
4. The preparation method according to any one of claims 1 to 3, wherein the preparation method of the sheet-shaped battery negative electrode sheet comprises the following steps:
mixing an active material of the battery negative pole piece with a conductive agent and a binder, then adding a solvent for dispersion to obtain negative pole slurry, then coating the negative pole slurry on a negative pole current collector, drying, rolling and die-cutting to obtain the sheet-shaped battery negative pole piece.
Preferably, in the preparation method of the sheet-shaped battery negative pole piece, the rolling pressure is 0-20 MPa, and the rolling time is 0-120 s.
Preferably, in the preparation method of the sheet-shaped battery negative electrode piece, the drying is preferably vacuum drying. Preferably, the drying temperature is 60-110 ℃, and preferably 70-100 ℃. Further, the drying time is 0.5-20 hours, preferably 12-20 hours.
Preferably, the battery negative pole piece is rolled and sliced to be made into a pole piece with the size required by a button or soft package battery.
Preferably, before the lithium sheet and/or the sodium sheet is attached to the battery negative pole piece, the lithium sheet and/or the sodium sheet is rolled into a lithium foil or a sodium foil with a smooth surface and a thickness of less than or equal to 200 mu m. Preferably, under the protection of inert atmosphere, the lithium sheet and/or the sodium sheet are rolled into lithium foil or sodium foil with smooth surface and thickness less than or equal to 200 mu m.
Preferably, the area of the rolled lithium sheet and/or sodium sheet is larger than that of the negative electrode sheet.
5. The method according to any one of claims 1 to 4, wherein the electrolyte is used in an amount of 20 to 400 μ L/cm 2 。
Preferably, the solute of the electrolyte is a lithium salt or a sodium salt.
Preferably, the lithium salt includes LiPF 6 、LiTFSI、LiBOB、LiClO 4 、LiFSI、LiBF 4 And LiAsF 6 At least one of; the sodium salt comprises NaPF 6 ，NaClO 4 At least one of NaTFSI and NaFSI.
Preferably, the solvent of the electrolyte includes two or three of Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DEC), diethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), and the like.
Preferably, the smooth surface of the lithium foil and/or the sodium foil faces the negative pole piece, and the lithium foil and/or the sodium foil completely covers and clings to the negative pole piece. Preferably, the attaching step is performed under protection of an inert atmosphere. Preferably, the pressure of the pressing is 0-2 MPa, and preferably 0.1-1 MPa.
Preferably, the standing time of the pressing is 0-120 min, and preferably 2-60 min.
Preferably, after the pre-lithiation and/or pre-sodium treatment, the voltage of the battery formed by the lithium foil and/or the sodium foil and the negative electrode plate is 1-2V, and preferably 1.2-1.7V.
6. The method according to any one of claims 1 to 5, further comprising a step of separating the pressed lithium foil and/or sodium foil from the negative electrode sheet, or adding a separator between the lithium foil and/or sodium foil and the negative electrode sheet.
Preferably, the preparation method further comprises the step of airing or washing the separated negative pole piece to remove the electrolyte remaining on the surface of the negative pole piece. Preferably, the washing solvent may be DMC.
Preferably, the preparation method further comprises the step of drying the washed negative pole piece.
7. A pre-lithiated, pre-sodiated composite negative electrode material prepared by the preparation method of any one of claims 1 to 6. Preferably, the composite anode material is a two-dimensional composite anode material.
8. Use of the pre-lithiated, pre-sodiated composite negative electrode material prepared by the preparation method of any one of claims 1 to 6 in a lithium battery or a sodium battery. Preferably as an application in a negative electrode of a lithium battery.
9. A lithium battery or a sodium battery, which is characterized by comprising the pre-lithiated and pre-sodiated composite negative electrode material and/or negative electrode sheet prepared by the preparation method of any one of claims 1 to 6. Preferably, the lithium battery or the sodium battery may be a half battery or a full battery. For example, the half-cell may be a 2032 button half-cell.
10. A lithium or sodium battery as claimed in claim 9, characterized in that the half-cell further comprises a lithium and/or sodium sheet.
Preferably, the half cell further comprises a separator. Preferably, the separator may be at least one of PP, PE, PP/PE/PP, glass fiber, and the like. More preferably, the separator is a single-sided and/or double-sided ceramic-coated separator. For example, the charge-discharge interval of the separator is 0.005 to 3V.
Preferably, the full cell further includes a positive electrode tab. Preferably, the positive electrode material of the positive electrode plate includes at least one of ternary positive electrode materials such as lithium cobaltate, lithium iron phosphate, sodium vanadium phosphate, cobalt nickel manganese and the like.
Preferably, the capacity ratio of the negative electrode to the positive electrode is 1.0 to 1.2.
Preferably, the full cell further includes an electrolyte and a separator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110234014.XA CN115036444A (en) | 2021-03-03 | 2021-03-03 | Pre-lithiation and pre-sodium-treatment composite negative electrode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110234014.XA CN115036444A (en) | 2021-03-03 | 2021-03-03 | Pre-lithiation and pre-sodium-treatment composite negative electrode material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115036444A true CN115036444A (en) | 2022-09-09 |
Family
ID=83118019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110234014.XA Pending CN115036444A (en) | 2021-03-03 | 2021-03-03 | Pre-lithiation and pre-sodium-treatment composite negative electrode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115036444A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115763947A (en) * | 2022-11-07 | 2023-03-07 | 南开大学 | Ampere-hour-grade sodium ion soft package battery |
| CN117169748A (en) * | 2023-10-19 | 2023-12-05 | 荣耀终端有限公司 | Detection method for gram capacity of lithium-supplementing electrode slice |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103996820A (en) * | 2014-05-30 | 2014-08-20 | 南京安普瑞斯有限公司 | Lithium ion battery as well as mixed positive electrode and active material with synergistic effect |
| KR20150014877A (en) * | 2013-07-30 | 2015-02-09 | 주식회사 엘지화학 | Pre-lithiation Method of Anode Electrodes |
| CN104538194A (en) * | 2014-12-18 | 2015-04-22 | 天津大学 | Preparation method of lithium ion capacitor (LIC) adopting pre-lithiation hard carbon negative electrode |
| CN108123101A (en) * | 2016-11-29 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of carbon group material using prelithiation does the lithium-sulfur cell and preparation method of cathode |
| CN110517902A (en) * | 2019-08-26 | 2019-11-29 | 福建翔丰华新能源材料有限公司 | Lithium-ion capacitor negative electrode material and preparation method thereof |
| WO2020076091A1 (en) * | 2018-10-10 | 2020-04-16 | 주식회사 엘지화학 | Method for manufacturing negative electrode for lithium secondary battery |
| CN111952545A (en) * | 2019-05-16 | 2020-11-17 | 同济大学 | Pre-lithiated lithium ion secondary battery negative electrode material and mechanical pre-lithiation method thereof |
| CN112125334A (en) * | 2019-06-24 | 2020-12-25 | 厦门稀土材料研究所 | Metal oxide/carbon intercalated layer two-dimensional composite material and preparation method and application thereof |
-
2021
- 2021-03-03 CN CN202110234014.XA patent/CN115036444A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150014877A (en) * | 2013-07-30 | 2015-02-09 | 주식회사 엘지화학 | Pre-lithiation Method of Anode Electrodes |
| CN103996820A (en) * | 2014-05-30 | 2014-08-20 | 南京安普瑞斯有限公司 | Lithium ion battery as well as mixed positive electrode and active material with synergistic effect |
| CN104538194A (en) * | 2014-12-18 | 2015-04-22 | 天津大学 | Preparation method of lithium ion capacitor (LIC) adopting pre-lithiation hard carbon negative electrode |
| CN108123101A (en) * | 2016-11-29 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of carbon group material using prelithiation does the lithium-sulfur cell and preparation method of cathode |
| WO2020076091A1 (en) * | 2018-10-10 | 2020-04-16 | 주식회사 엘지화학 | Method for manufacturing negative electrode for lithium secondary battery |
| CN111952545A (en) * | 2019-05-16 | 2020-11-17 | 同济大学 | Pre-lithiated lithium ion secondary battery negative electrode material and mechanical pre-lithiation method thereof |
| CN112125334A (en) * | 2019-06-24 | 2020-12-25 | 厦门稀土材料研究所 | Metal oxide/carbon intercalated layer two-dimensional composite material and preparation method and application thereof |
| CN110517902A (en) * | 2019-08-26 | 2019-11-29 | 福建翔丰华新能源材料有限公司 | Lithium-ion capacitor negative electrode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JUSEF HASSOUN，等: ""A contribution to the progress of high energy batteries: A metal-free, lithium-ion, silicon–sulfur battery"", 《JOURNAL OF POWER SOURCES》, vol. 202, pages 308 - 313 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115763947A (en) * | 2022-11-07 | 2023-03-07 | 南开大学 | Ampere-hour-grade sodium ion soft package battery |
| CN115763947B (en) * | 2022-11-07 | 2023-06-16 | 南开大学 | Anshi sodium ion soft package battery |
| CN117169748A (en) * | 2023-10-19 | 2023-12-05 | 荣耀终端有限公司 | Detection method for gram capacity of lithium-supplementing electrode slice |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111129502B (en) | Negative pole piece and secondary battery | |
| US11114659B2 (en) | Negative electrode sheet and secondary battery | |
| RU2631239C2 (en) | Method of producing a layer of active material of positive electrode for lithium-ion battery and layer of active material of positive electrode for lithium-ion accumulator | |
| CN110854382A (en) | Positive electrode lithium supplement material, positive electrode containing positive electrode lithium supplement material and preparation method of positive electrode lithium supplement material | |
| CN111900501A (en) | Lithium supplement additive and preparation method and application thereof | |
| EP3480878A1 (en) | Positive electrode additive and preparation method therefor, positive electrode plate and secondary lithium ion battery | |
| KR20220036961A (en) | Secondary batteries, battery modules including secondary batteries, battery packs and devices | |
| CN111969182B (en) | Positive pole piece, preparation method thereof, and lithium ion secondary battery, electric vehicle and electronic product related to positive pole piece | |
| CN116646588B (en) | Sodium ion battery, battery module, battery pack and electricity utilization device | |
| CN115036444A (en) | Pre-lithiation and pre-sodium-treatment composite negative electrode material and preparation method and application thereof | |
| CN111883765A (en) | Lithium battery positive active material, preparation method thereof and lithium battery | |
| US20220310988A1 (en) | Positive electrode plate, and electrochemical apparatus and electronic apparatus containing such positive electrode plate | |
| US20220320500A1 (en) | Electrochemical device and an electronic device | |
| EP3890089A1 (en) | Lithium metal battery | |
| CN115663114A (en) | Negative plate, preparation method of negative plate and battery | |
| WO2022198614A1 (en) | Negative electrode material, preparation method therefor, electrochemical device, and electronic device | |
| EP4089766B1 (en) | Positive electrode plate, electrochemical device comprising same, and electronic device | |
| CN115207335A (en) | Low-temperature chargeable and dischargeable lithium ion battery cathode material and lithium ion battery | |
| CN114175343A (en) | Secondary battery and device containing the same | |
| CN110611117A (en) | Lithium ion battery and positive pole piece | |
| WO2022195716A1 (en) | Separator, lithium ion secondary battery, and methods for producing same | |
| WO2024087013A1 (en) | Electrode assembly, battery cell, battery and electric device | |
| CN116632368B (en) | Secondary battery and electronic device | |
| CN116613390B (en) | Battery and electronic equipment | |
| US20220223854A1 (en) | Negative electrode material and electrochemical apparatus and electronic apparatus containing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |