CN115417754A - Nano lithium squarate, preparation method, positive plate and lithium battery - Google Patents
Nano lithium squarate, preparation method, positive plate and lithium battery Download PDFInfo
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- CN115417754A CN115417754A CN202210977478.4A CN202210977478A CN115417754A CN 115417754 A CN115417754 A CN 115417754A CN 202210977478 A CN202210977478 A CN 202210977478A CN 115417754 A CN115417754 A CN 115417754A
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- SOCJEFTZDJUXNO-UHFFFAOYSA-L lithium squarate Chemical compound [Li+].[Li+].[O-]C1=C([O-])C(=O)C1=O SOCJEFTZDJUXNO-UHFFFAOYSA-L 0.000 title claims abstract description 134
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 73
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 29
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 26
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 238000001953 recrystallisation Methods 0.000 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 239000002482 conductive additive Substances 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 238000006138 lithiation reaction Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 10
- 230000002427 irreversible effect Effects 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 29
- 229910001416 lithium ion Inorganic materials 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 24
- 239000002002 slurry Substances 0.000 description 21
- 238000002156 mixing Methods 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000006258 conductive agent Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000002033 PVDF binder Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000004080 punching Methods 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- -1 nickel cobalt aluminum Chemical compound 0.000 description 7
- 239000006230 acetylene black Substances 0.000 description 6
- 239000013589 supplement Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- ZQCQTPBVJCWETB-UHFFFAOYSA-N 4-fluoro-1,3-dioxol-2-one Chemical compound FC1=COC(=O)O1 ZQCQTPBVJCWETB-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- IHXWECHPYNPJRR-UHFFFAOYSA-N 3-hydroxycyclobut-2-en-1-one Chemical compound OC1=CC(=O)C1 IHXWECHPYNPJRR-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- UNUVOQUVNRHMOA-UHFFFAOYSA-L sodium squarate Chemical compound [Na+].[Na+].[O-]C1=C([O-])C(=O)C1=O UNUVOQUVNRHMOA-UHFFFAOYSA-L 0.000 description 2
- 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 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 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 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- PWEBUXCTKOWPCW-UHFFFAOYSA-L squarate Chemical compound [O-]C1=C([O-])C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/703—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups
- C07C49/707—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups a keto group being part of a three- to five-membered ring
-
- 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
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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
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/04—Systems containing only non-condensed rings with a four-membered ring
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The application provides a nano squaric acid lithium and a preparation method thereof, a positive plate and a lithium battery, wherein the preparation method of the nano squaric acid lithium comprises the following steps: dissolving squaric acid and a lithium-containing compound in deionized water, stirring, drying to obtain lithium squarate powder, and performing recrystallization precipitation treatment on the lithium squarate powder to obtain nano lithium squarate powder. According to the application, the nano squaric acid lithium is added into the positive plate as a pre-lithiation material, so that the irreversible lithium loss in the first charge-discharge process of the lithium battery is compensated, and the overall capacity of the battery is further improved; for constructing a cathode-free lithium metal battery with practical value, the nano lithium squarate can provide an additional lithium source for a cathode, and the energy density and the cycling stability of the cathode-free lithium metal battery are improved.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a preparation method of nano squaric acid lithium serving as a pre-lithiation additive of a positive electrode, nano squaric acid lithium prepared by the preparation method, a positive plate prepared by applying the nano squaric acid lithium and a lithium ion battery.
Background
The lithium ion battery which operates in an ion insertion/extraction working mode and the lithium metal battery which operates in a deposition/dissolution working mode of metal lithium and has higher energy density take lithium loss caused by a solid electrolyte intermediate phase in the first charging process, and the lithium ion battery is particularly obvious in performance of high-capacity negative electrode materials (such as silicon, tin and the like). The main means of prelithiation today include negative prelithiation and positive prelithiation. The pre-lithiation of the negative electrode has high requirements on working environment or the method is complex and is accompanied with certain toxicity, and the pre-lithiation of the positive electrode has the advantages of easiness in synthesis, low price and the like. Lithium squarate (chemical formula is Li) 2 C 4 O 4 ) The theoretical charging specific capacity is 425mAh g < -1 >, the theoretical decomposition potential is 4.0V, the decomposition products of the electrochemical reaction mainly comprise carbon dioxide gas and carbon, impurities which interfere the electrochemical reaction of a system cannot be introduced, and the lithium ion battery anode pre-lithiation reagent is an ideal anode pre-lithiation reagent. However, the squarylium salt has low conductivity and ion mobility, and the shape and the granularity of particles of the squarylium salt need to be optimized in the practical application process to reduce the voltage platform of the squarylium salt, so that the lithium capacity of the squarylium salt is fully exerted.
CN110683944A discloses a squarate and a preparation method and application thereof, and provides a lithium squarate prepared by a method of mixing in an organic solvent or mixing by a grinding method and used as a lithium supplement agent of a lithium ion battery anode material, but the agglomeration phenomenon of primary particles is serious, and the particle size of the whole lithium supplement agent is in a micron-scale range, so that the initial decomposition potential of the lithium squarate is high, and the application of the lithium squarate in a low-voltage platform anode material is limited.
CN113443973A discloses a lithium squarate, a preparation method and an application thereof, wherein the lithium squarate is prepared from an aqueous solution, and is combined with a freeze drying method to further reduce the particle size of the lithium squarate to a nanometer level, so that the decomposition potential of the lithium squarate can be reduced, the capacity exertion of the lithium squarate can be improved, and the lithium squarate is used as a positive pole lithium supplement agent to be applied to a lithium ion battery and a lithium sulfur battery. However, the freeze-drying preparation method has high cost, and the process conditions are not favorable for large-scale batch production.
Disclosure of Invention
In view of the above, the present application provides a nano lithium squarate, a preparation method thereof, a positive plate and a lithium battery.
The invention adopts the following technical scheme: dissolving squaric acid and a sodium-containing compound in deionized water, stirring, drying to obtain lithium squarate powder, and recrystallizing and separating the lithium squarate powder to obtain nano lithium squarate powder.
In some embodiments, the lithium-containing compound is one or more of lithium carbonate, lithium bicarbonate, lithium hydroxide, lithium phosphate.
In some embodiments, the molar ratio of the squaraine to the lithium-containing compound is 0.5 to 5.
In some embodiments, the stirring time is 1 to 48 hours, and the drying temperature is 80 to 240 ℃.
In some embodiments, the method of recrystallization deposition comprises: dissolving the lithium squarate powder in deionized water to obtain a lithium squarate solution; and adding an organic solvent into the lithium squarate solution, stirring, precipitating crystals, performing suction filtration, and drying filter residues to obtain the nano lithium squarate.
In some embodiments, the organic solvent is one or more of absolute ethanol, tetrahydrofuran, N-methylpyrrolidone, acetone, N-dimethylformamide.
In some embodiments, the rate of addition of organic solvent to the lithium squarate solution is from 1 to 20 μ L/min.
In some embodiments, the mass ratio of the lithium squarate powder to the deionized water is 1 to 100, and the mass ratio of the deionized water to the organic solvent is 20 to 200.
In some embodiments, the nano lithium squarate has an average particle size of 100 to 500nm.
The application also provides nano lithium squarate which is prepared by the preparation method of the nano lithium squarate.
The application also provides a positive plate, which comprises a positive material, a conductive additive and a binder, and the positive plate further comprises the nano lithium squarate.
The application also provides a lithium battery, which comprises the positive plate.
The nano Fang Suanli prepared by the method has uniform particle structure distribution. The nano lithium squarate is added into the positive plate as a prelithiation material, and has excellent compatibility with a solvent used in slurry required for forming the positive plate. Meanwhile, according to the actual requirement of the negative electrode, nano lithium squarate with different contents can be added into the positive plate, so that the high-efficiency lithium supplement of the negative electrode materials of the lithium ion battery and the lithium metal battery is realized, and the cycle life and the capacity of the lithium battery can be effectively prolonged. Compared with a lithium ion half-cell without the nano lithium squarate, the lithium ion half-cell with the nano lithium squarate has higher first-time charging specific capacity and first-time charging and discharging coulombic efficiency, and has proper decomposition potential (less than 5V). Meanwhile, the lithium ion battery can be used as an additional negative electrode lithium source supplement to construct a lithium metal full battery without a negative electrode, and the cycle stability and the energy density of the lithium metal full battery are improved. Meanwhile, the preparation method is synthesized in the aqueous solvent, the whole process is simple, controllable, nontoxic, low in cost, environment-friendly and suitable for mass production.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of lithium squarate prepared in comparative example 1 of the present invention.
FIG. 2 is an SEM image of recrystallized nano lithium squarate prepared in example 1 of the present invention.
FIG. 3 is an SEM image of recrystallized nano lithium squarate prepared in example 3 of the present invention.
FIG. 4 is an X-ray diffraction (XRD) pattern of lithium squarate prepared according to comparative example 1 of the present invention.
Fig. 5 is a graph showing a half-cell voltage curve of lithium squarate prepared in comparative example 1 of the present invention.
FIG. 6 is a graph of the half-cell voltage curve for recrystallized nano lithium squarate prepared in example 1 of the present invention.
FIG. 7 is a graph of the half-cell voltage curve for recrystallized nano lithium squarate prepared in example 2 of the present invention.
Fig. 8 is a graph of the half-cell voltage profile of recrystallized nano lithium squarate prepared in example 3 of the present invention.
FIG. 9 is a graph showing the voltage profile of a full cell in which lithium nano-squarate is not added to a positive electrode sheet in comparative example 2 according to the present invention.
FIG. 10 is a graph of the full cell voltage of recrystallized nano lithium squarate prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiments of this application belong. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the embodiments of the present application.
Some embodiments of the present application will be described in detail below with reference to the accompanying drawings. In the following embodiments, features of the embodiments may be combined with each other without conflict.
The application provides a preparation method of nano lithium squarate, which comprises the following steps:
s1, dissolving squaric acid and a lithium-containing compound in water, stirring and drying to obtain lithium squarate powder, wherein the lithium-containing compound can be one or more of lithium carbonate, lithium bicarbonate, lithium hydroxide and lithium phosphate, and the molar ratio of the squaric acid to the lithium-containing compound can be 0.5-5.
In the process, the squaric acid and the lithium-containing compound are dissolved in water, so that the squaric acid and the lithium-containing compound are fully reacted, and then the mixture is stirred and dried to obtain the lithium squarate powder. Wherein the molar ratio of the squaraine to the lithium-containing compound is 0.5 to 5, and the sufficient reaction of the lithium-containing compound can be ensured in the range. If the content of the squaric acid is excessive, the excessive squaric acid can be mixed into the lithium squarate to act with an electrolyte in a lithium battery, so that the performance of the battery is reduced; if the content of the lithium-containing compound is too high, the prepared lithium supplement agent can influence the electrochemical performance of the positive plate.
In some embodiments, the stirring time may be 4 to 48 hours when the squaraine reacts with the lithium-containing compound, so that the two react sufficiently in water, and the drying temperature may be 80 to 240 ℃ to remove water.
S2, carrying out recrystallization precipitation treatment on the squaric acid lithium powder obtained in the step S1 to obtain nano squaric acid lithium.
The recrystallization and precipitation of the lithium squarate powder obtained in the step S1 specifically comprises the following steps:
s21, dissolving the lithium squarate powder in deionized water to obtain a lithium squarate solution. In the process, the mass ratio of the lithium squarate powder to the deionized water can be 0.02-2, and the lithium squarate powder can be completely dissolved in the deionized water in the range.
S22, slowly adding an organic solvent into the squaric acid lithium solution, stirring, separating out crystals, performing suction filtration, and drying filter residues to obtain nanometer Fang Suanli, wherein the average particle size of the nanometer lithium squarate is 100-500 nm.
In the process, because the solubility of Fang Suanli in the organic solvent is extremely low, the slow precipitation process inhibits the continuous growth and crystallization of lithium squarate particles along with the slow addition of the organic solvent, and meanwhile, in the precipitation process of lithium squarate crystals, the high-speed stirring can ensure that the precipitated lithium squarate particles have better dispersibility, and finally the lithium squarate crystals with the nanometer-level particle size are obtained.
Meanwhile, because the solubility of the lithium squarate in the lithium squarate powder is different from that of other impurities in the organic solvent, the organic solvent can purify the lithium squarate, remove the impurities and other components in the lithium squarate powder and improve the purity of the lithium squarate.
In some embodiments, the mass ratio of the deionized water to the organic solvent in the lithium squarate solution may be 20 to 200, and the organic solvent may be one or more of absolute ethanol, tetrahydrofuran, N-methylpyrrolidone, acetone, and N, N-dimethylformamide. The organic reagents listed above have wide sources of raw materials, are cheap and are beneficial to industrial application.
In some embodiments, the rate of addition of the organic solvent to the lithium squarate solution may be 1 to 20 μ L/min.
In the preparation process, the lithium squarate is synthesized in the hydrosolvent, and the nano lithium squarate is obtained by a recrystallization method, so that the whole preparation process is simple, controllable, environment-friendly and suitable for mass production. Meanwhile, the nano lithium squarate serving as the pre-lithiation material can be directly added into the anode slurry without additional operation procedures or modification of adding equipment, so that the method has a very good practical application prospect.
The application also provides nano lithium squarate prepared by the preparation method.
The application also provides a positive plate, which comprises a positive material, a conductive additive, a binder and a pre-lithiation material, wherein the pre-lithiation material is nano lithium squarate.
Mixing the positive electrode material, the conductive additive, the binder and the nano lithium squarate, adding a solvent, stirring to obtain slurry, coating the slurry on an aluminum foil, drying, rolling a film and punching to obtain the positive electrode plate containing the pre-lithiation material.
The positive electrode material can comprise one or more of lithium iron phosphate, lithium manganese iron phosphate, lithium nickelate, lithium manganate, lithium cobaltate, lithium nickel manganate, ternary nickel cobalt manganese, ternary nickel cobalt aluminum and lithium sulfide. The conductive agent can be one or more of carbon black, carbon nano tubes, graphene and carbon nano-fiber carbon-containing materials; the binder comprises a high polymer material, and can be one or more of polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polyvinylpyrrolidone (PVP), sodium carboxymethylcellulose (CMC) and sodium alginate; the solution may be one or more of deionized water, NMP, tetrahydrofuran, polytetrafluoroethylene, and the like.
In some embodiments, the mass ratio of the nano lithium squarate to the positive electrode material may be 0.01 to 0.2, the mass ratio of the lithium battery positive electrode material to the conductive agent may be 0.1 to 10, and the mass ratio of the conductive agent to the binder may be 1 to 10.
The application also provides a lithium battery, which comprises the positive plate. Lithium batteries include lithium ion batteries and lithium metal batteries.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by persons skilled in the art that the following examples are illustrative only and are not to be construed as limiting the invention. Reagents, software and equipment not specifically submitted to the following examples are conventional commercial products or open sources unless otherwise submitted.
Example 1
Preparing lithium squarate powder: mixing squaric acid and lithium carbonate in a molar ratio of 1.05:1 into deionized water, wherein the mass ratio of the squaric acid to the water is 1: and (30) stirring for 12 hours, and drying for 12 hours at the drying temperature of 90 ℃ to obtain the lithium squarate powder.
Recrystallizing and separating out to obtain nanometer Fang Suanli: dissolving the lithium squarate powder in deionized water, wherein the mass ratio of the lithium squarate powder to the deionized water is 1: and 30, adding absolute ethyl alcohol into the lithium squarate solution at the speed of 10 mu L/min, wherein the mass ratio of the deionized water to the absolute ethyl alcohol is 40:1, stirring for 2 hours at room temperature, performing suction filtration to obtain filter residue, and drying the filter residue at 100 ℃ for 24 hours to obtain nano lithium squarate powder.
Preparing a lithium ion half cell: mixing nano lithium squarate powder, acetylene black conductive agent and PVDF binder in a proportion of 60:30:10, adding NMP solvent, stirring to obtain slurry, coating the slurry on a metal aluminum foil, drying, and punching to obtain the positive plate.
The positive plate is used as a positive electrode, a metal lithium foil is used as a negative plate, a polypropylene microporous membrane (Celgard 2400) is used as a diaphragm, the negative plate, the diaphragm and the positive plate are assembled into a 2032 type button cell in a glove box filled with high-purity argon, wherein the electrolyte component is that lithium salt of lithium hexafluorophosphate of 1mol/L is dissolved in a methyl ethyl carbonate/diethyl carbonate/fluoroethylene carbonate solvent (volume ratio 1.
Preparing a lithium ion-lithium metal hybrid full battery with a lithium-free negative electrode: the lithium metal full battery comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the diaphragm and the electrolyte are arranged between the positive plate and the negative plate, and the positive-negative capacity ratio is controlled to be 1.25. The specific conditions are as follows: mixing the nano lithium squarate powder obtained in the embodiment with a nickel-cobalt-manganese ternary positive electrode material, an acetylene black conductive agent and a PVDF binder according to the weight ratio of 5:75:10:10, adding an NMP solvent after mixing, stirring to obtain a slurry, coating the slurry on a metal aluminum foil, drying, and punching to obtain the positive plate.
Mixing graphite, a carbon black conductive agent and a PVDF binder in a ratio of 9:0.3: dissolving the components in NMP in a mass ratio of 0.7, fully stirring to prepare slurry, coating the slurry on a metal copper foil, and drying and punching to obtain the modified negative current collector.
The modified negative current collector is directly used as a negative plate, celgard 2400 is used as a diaphragm, 1mol/L lithium salt of lithium hexafluorophosphate is dissolved in a methyl ethyl carbonate/diethyl carbonate/fluoroethylene carbonate solvent (volume ratio 1.
Example 2
Preparing lithium squarate powder: mixing squaric acid and lithium bicarbonate in a molar ratio of 1.2:1 in deionized water, wherein the mass ratio of the squaric acid to the water is 1: and (30) stirring for 12 hours, and drying for 12 hours at the drying temperature of 90 ℃ to obtain the lithium squarate powder.
Recrystallizing and separating out to obtain nanometer Fang Suanli: dissolving the lithium squarate powder in deionized water, wherein the mass ratio of the lithium squarate powder to the deionized water is 1: and 30, adding absolute ethyl alcohol into the lithium squarate solution at the speed of 10 mu L/min, wherein the mass ratio of the deionized water to the absolute ethyl alcohol is 60:1, stirring for 2 hours at room temperature, performing suction filtration to obtain filter residue, and drying the filter residue at 120 ℃ for 24 hours to obtain nano lithium squarate powder.
Preparing a lithium ion half cell: mixing nano lithium squarate powder, acetylene black conductive agent and PVDF binder in a proportion of 30:60:10, adding NMP solvent, stirring to obtain slurry, coating the slurry on a metal aluminum foil, drying, and punching to obtain the positive plate. The positive electrode sheet was assembled into a lithium ion half cell in the same manner as in example 1.
Preparing a lithium ion full battery: the lithium ion full cell comprises a positive plate, a negative electrode, a diaphragm and electrolyte, wherein the diaphragm and the electrolyte are arranged between the positive plate and the negative electrode. Wherein, the positive-negative electrode capacity ratio is controlled to be 0.91. The specific conditions are as follows: mixing the lithium squarate powder obtained in the embodiment with a nickel-cobalt-manganese ternary positive electrode material, an acetylene black conductive agent and a PVDF binder according to the weight ratio of 5:75:10:10, adding an NMP solvent after mixing, stirring to obtain a slurry, coating the slurry on a metal aluminum foil, drying, and punching to obtain the positive plate.
Mixing artificial graphite, a carbon black conductive agent and a PVDF binder in a ratio of 8:1: dissolving the powder 1 in NMP, fully stirring to prepare slurry, coating the slurry on a metal copper foil, drying and punching to obtain the negative electrode.
A 2032 type button cell was assembled by using Celgard 2400 as a separator, and 1mol/L lithium hexafluorophosphate salt dissolved in a methyl ethyl carbonate/diethyl carbonate/fluoroethylene carbonate solvent (volume ratio 1.
Example 3
Preparing lithium squarate powder: dissolving squaric acid and lithium hydroxide in a molar ratio of 1:2 in deionized water, wherein the mass ratio of the squaric acid to the water is 1: and (30) stirring for 12 hours, and drying for 12 hours at the drying temperature of 90 ℃ to obtain the lithium squarate powder.
Recrystallizing and separating out to obtain nanometer Fang Suanli: dissolving the lithium squarate powder in deionized water, wherein the mass ratio of the lithium squarate powder to the deionized water is 1: and 30, adding absolute ethyl alcohol into the lithium squarate solution at the speed of 10 mu L/min, wherein the mass ratio of the deionized water to the absolute ethyl alcohol is 25:1, stirring for 2 hours at room temperature, performing suction filtration to obtain filter residue, and drying the filter residue at 100 ℃ for 24 hours to obtain nano lithium squarate powder.
Preparing a lithium ion half cell: mixing nano lithium squarate powder, acetylene black conductive agent and PVDF binder in a proportion of 60:30:10, adding NMP solvent, stirring to obtain slurry, coating the slurry on a metal aluminum foil, drying, and punching to obtain the positive plate. The positive electrode sheet was assembled into a lithium ion half cell in the same manner as in example 1.
Preparing a lithium ion full battery: the lithium ion full cell includes a positive electrode sheet, a negative electrode, and a separator and an electrolyte disposed between the positive electrode sheet and the negative electrode. Wherein, the positive-negative electrode capacity ratio is controlled to be 0.90. The specific conditions are as follows: mixing the lithium squarate powder obtained in the embodiment with a lithium iron phosphate positive electrode material, an acetylene black conductive agent and a PVDF binder according to a ratio of 8:72:10:10, adding an NMP solvent after mixing, stirring to obtain a slurry, coating the slurry on a metal aluminum foil, drying, and punching to obtain the positive plate.
Mixing a silicon-carbon composite material, a carbon black conductive agent and a PVDF binder in a ratio of 8:1: dissolving the powder 1 in NMP, fully stirring to prepare slurry, coating the slurry on a metal copper foil, drying and punching to obtain the negative electrode.
A 2032 type button cell was assembled by using Celgard 2400 as a separator, and 1mol/L lithium hexafluorophosphate salt dissolved in a methyl ethyl carbonate/diethyl carbonate/fluoroethylene carbonate solvent (volume ratio 1.
Comparative example 1
Comparative example 1 is different from example 1 in that sodium squarate powder in the lithium ion half cell prepared was not subjected to recrystallization precipitation treatment. The rest of the procedure was the same as in example 1.
Comparative example 2
Comparative example 2 is different from example 1 in that the positive electrode sheet of the prepared lithium ion-lithium metal hybrid type full cell was not added with nano Fang Suanli, and the remaining procedure was the same as example 1.
Comparative example 3
Comparative example 3 is different from example 2 in that the nano-grade Fang Suanli is not added to the positive electrode sheet in the prepared lithium ion full cell, and the rest of the procedure is the same as example 2.
Comparative example 4
Comparative example 3 is different from example 3 in that the nano-grade Fang Suanli is not added to the positive electrode sheet in the prepared lithium ion full cell, and the rest of the procedure is the same as example 3.
Referring to fig. 1 and 2, the present application also performed scanning electron microscope tests on the lithium squarate powder and nano lithium squarate powder of comparative example 1 and example 1. In FIG. 1, the lithium squarate powder has a large particle size ranging from 2 to 5 μm and significant agglomeration. In figure 2, the nanometer Fang Suanna is spherical granular, the particle size is obviously reduced within the range of 0.1-1 μm, and the dispersibility is better.
Referring to fig. 3, the present application also performed a scanning electron microscope test on the nano lithium squarate powder of example 3, in fig. 3, the nano lithium squarate mainly has a morphology of spherical particle aggregation, and the particle size is in the range of 500nm, and part of the nano lithium squarate is aggregated into a sheet shape. As can be seen from fig. 1 to 3, the particles of the lithium squarate powder are nano-sized and distributed more uniformly by recrystallization.
Meanwhile, referring to fig. 4, the application also performs XRD test on the lithium squarate powder in comparative example 1, and the characteristic peak of the synthesized lithium squarate powder is consistent with the standard card spectrogram of lithium squarate, which proves that the lithium squarate is successfully synthesized.
The lithium ion half cells prepared in the above examples 1 to 3 and comparative example 1 were subjected to a constant current charge and discharge performance test using a Land (blue) battery test system at room temperature. The current density is 500mA/g, and the charge-discharge voltage range is 2.5-4.0V.
TABLE 1 electrochemical Performance of lithium-ion half-cells prepared in comparative example 1 and examples 1 to 3
Referring to fig. 5 to 8 in combination with table 1, it can be seen that, compared to comparative example 1, sodium squarate powder is separated out through recrystallization, and the first charge specific capacity, the first discharge specific capacity, and the first discharge coulombic efficiency of the half-cell are improved.
The present application also performs a constant current charge and discharge performance test on the lithium ion-lithium metal hybrid type full cell having no lithium at the negative electrode in the above example 1 and comparative example 2 using a Land (blue) battery test system at room temperature. The first circle of the battery has the charge-discharge current density of 0.1C and the charge-discharge voltage range of 2.5-5.0V. In the circulation after the second circle, the current density is 0.5C, and the charge-discharge voltage range is 2.5-4.3V.
Referring to fig. 9 and 10, voltage profiles of hybrid full cells prepared without the nano Fang Suanli positive prelithiation additive of comparative example 2 and the nano lithium squarate containing positive prelithiation additive of example 1 are shown, respectively. In comparison with FIG. 9, in FIG. 10, the initial charge specific capacity was 249.3mAh g obtained from comparative example 2 due to the addition of the prelithiation material containing nano lithium squarate -1 Increased to 277.9mAh g -1 Reversible specific Capacity 202.1mAh g from comparative example 2 -1 Lifting to 211.4mAh g - 1, the first irreversible lithium loss is obviously reduced, and the subsequent cycle capacity and energy density of the full battery are improved. Meanwhile, after the hybrid full cell prepared in example 1 was circulated in a commercial ester electrolyte for 70 cycles, the reversible specific capacity was 96.5mAh g compared to that of comparative example 2 under the same conditions -1 Still maintains higher reversible specific capacity of 141.6mAh g -1 And the addition of the nano lithium squarate is proved to improve the cycle capacity and the energy density of the hybrid full battery.
Meanwhile, the lithium ion-lithium metal hybrid full battery with the lithium-free negative electrode avoids the excessive use of metal lithium on the negative electrode side, reduces the using amount of graphite on the negative electrode side, and effectively improves the mass energy density and the volume energy density of a battery system. In addition, the battery system can directly apply equipment conditions for manufacturing the conventional lithium ion battery, brings great convenience and cost saving for the assembly of the battery, and has important industrial significance for developing a high-energy-density lithium metal battery system.
And (3) carrying out a blue test on the lithium ion full batteries in comparative examples 3 and 4 and examples 2 and 3 at room temperature, wherein the charge-discharge current density of the first circle of the battery is 0.1C, and the charge-discharge voltage range is 2.8-5.0V. In the circulation after the second circle, the current density is 1C, and the charging and discharging voltage range is 2.8-4.3V.
Table 2 electrochemical performance of lithium ion full cells prepared in comparative examples 3 and 4 and examples 2 and 3
As can be seen from table 2, the addition of the nano lithium squarate can effectively improve the first charge capacity and coulombic efficiency of the lithium ion full battery, reduce the first irreversible lithium loss, and improve the subsequent cycle capacity and energy density of the full battery.
Although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention.
Claims (12)
1. A preparation method of nano lithium squarate is characterized by comprising the following steps:
dissolving squaric acid and a lithium-containing compound in deionized water, stirring and reacting, evaporating the solvent, and drying to obtain lithium squarate powder;
and recrystallizing the lithium squarate powder to separate out the lithium squarate powder to obtain the nano lithium squarate powder.
2. The method for preparing nano lithium squarate according to claim 1, wherein the lithium-containing compound is one or more of lithium carbonate, lithium bicarbonate, lithium hydroxide and lithium phosphate.
3. The method for preparing nano lithium squarate according to claim 1, wherein the molar ratio of the squaric acid to the lithium-containing compound is 0.5 to 5.
4. The method for preparing nano lithium squarate according to claim 1, wherein the stirring time is 1 to 48 hours, and the drying temperature is 80 to 240 ℃.
5. The method for preparing nano lithium squarate according to claim 1, wherein the recrystallization precipitation method comprises:
dissolving the lithium squarate powder in deionized water to obtain a lithium squarate solution;
and adding an organic solvent into the lithium squarate solution, stirring, precipitating crystals, filtering, and drying filter residues to obtain the nano lithium squarate.
6. The method for preparing nano lithium squarate according to claim 5, wherein the organic solvent is one or more of absolute ethyl alcohol, tetrahydrofuran, N-methyl pyrrolidone, acetone and N, N-dimethylformamide.
7. The method for preparing nano lithium squarate according to claim 5, wherein the rate of adding the organic solvent to the lithium squarate solution is 1 to 20 μ L/min.
8. The method for preparing nano lithium squarate according to claim 5, wherein in the lithium squarate solution, the mass ratio of the lithium squarate powder to the deionized water is 1-100, and the mass ratio of the deionized water to the organic solvent is 20-200.
9. The method for preparing nano lithium squarate according to claim 5, wherein the average particle diameter of the nano lithium squarate is 100 to 500nm.
10. A nano lithium squarate produced by the method for producing nano lithium squarate according to any one of claims 1 to 9.
11. A positive electrode sheet comprising a positive electrode material, a conductive additive and a binder, characterized in that the positive electrode sheet further comprises nano lithium squarate according to claim 10.
12. A lithium battery comprising the positive electrode sheet according to claim 11.
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