CN118198274B - Aqueous slurry polyanion sodium ion soft pack battery and preparation method thereof - Google Patents
Aqueous slurry polyanion sodium ion soft pack battery and preparation method thereof Download PDFInfo
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- CN118198274B CN118198274B CN202410401660.4A CN202410401660A CN118198274B CN 118198274 B CN118198274 B CN 118198274B CN 202410401660 A CN202410401660 A CN 202410401660A CN 118198274 B CN118198274 B CN 118198274B
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- sodium
- positive electrode
- sodium ion
- electrode plate
- ion soft
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 78
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000002002 slurry Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229920000447 polyanionic polymer Polymers 0.000 title claims abstract description 17
- 239000011734 sodium Substances 0.000 claims abstract description 65
- 239000007774 positive electrode material Substances 0.000 claims abstract description 37
- 239000011230 binding agent Substances 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims description 47
- 229910019142 PO4 Inorganic materials 0.000 claims description 38
- 229910052708 sodium Inorganic materials 0.000 claims description 36
- 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 claims description 35
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 17
- 229910052787 antimony Inorganic materials 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 239000010406 cathode material Substances 0.000 claims description 13
- 239000011888 foil Substances 0.000 claims description 13
- 229910021385 hard carbon Inorganic materials 0.000 claims description 13
- -1 vanadyl phosphate Chemical compound 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 11
- AEBYJSOWHQYRPK-UHFFFAOYSA-N 1,1'-biphenyl;sodium Chemical compound [Na].C1=CC=CC=C1C1=CC=CC=C1 AEBYJSOWHQYRPK-UHFFFAOYSA-N 0.000 claims description 10
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- 239000012002 vanadium phosphate Substances 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 239000011775 sodium fluoride Substances 0.000 claims description 9
- 235000013024 sodium fluoride Nutrition 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 7
- 238000010030 laminating Methods 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 claims description 5
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- KELHQGOVULCJSG-UHFFFAOYSA-N n,n-dimethyl-1-(5-methylfuran-2-yl)ethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=C(C)O1 KELHQGOVULCJSG-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 238000004146 energy storage Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 22
- 239000011149 active material Substances 0.000 description 21
- 238000001035 drying Methods 0.000 description 19
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 239000001768 carboxy methyl cellulose Substances 0.000 description 14
- 238000005520 cutting process Methods 0.000 description 14
- 238000005096 rolling process Methods 0.000 description 14
- 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 13
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 13
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 13
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 12
- 239000006245 Carbon black Super-P Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 229920003048 styrene butadiene rubber Polymers 0.000 description 11
- 238000005245 sintering Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000009616 inductively coupled plasma Methods 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 238000003466 welding Methods 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 239000002985 plastic film Substances 0.000 description 5
- 229920006255 plastic film Polymers 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- DEIVNMVWRDMSMJ-UHFFFAOYSA-N hydrogen peroxide;oxotitanium Chemical compound OO.[Ti]=O DEIVNMVWRDMSMJ-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 3
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical group FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical group [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M10/058—Construction or manufacture
- H01M10/0583—Construction or manufacture of accumulators with folded construction elements except wound ones, i.e. folded positive or negative electrodes or separators, e.g. with "Z"-shaped electrodes or separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/105—Pouches or flexible bags
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了一种水系浆料聚阴离子型钠离子软包电池及其制备方法，涉及新能源材料与器件技术领域。本发明钠离子软包电池的正极极片中采用化学式为Na3V2‑x‑ySbxTiyO(PO4)2F2的聚阴离子型正极材料；其中，0<x≤0.2，0<y≤0.2，在此基础上，可进一步采用水系粘结剂进行极片的制作，具有环保、成本低的显著优势。本发明制备的钠离子软包电池倍率性能优异，循环寿命长，可广泛应用于大规模储能以及新能源汽车等领域。
The present invention discloses an aqueous slurry polyanion sodium ion soft pack battery and a preparation method thereof, and relates to the technical field of new energy materials and devices. The positive electrode plate of the sodium ion soft pack battery of the present invention adopts a polyanion positive electrode material with a chemical formula of Na 3 V 2‑x‑y Sb x Ti y O(PO 4 ) 2 F 2 ; wherein 0<x≤0.2, 0<y≤0.2, and on this basis, an aqueous binder can be further used to make the plate, which has the significant advantages of environmental protection and low cost. The sodium ion soft pack battery prepared by the present invention has excellent rate performance and long cycle life, and can be widely used in large-scale energy storage and new energy vehicles and other fields.
Description
Technical Field
The invention relates to the technical field of new energy materials and devices, in particular to a water-based slurry polyanion type sodium ion soft-package battery and a preparation method thereof.
Background
The use of efficient electrochemical energy storage technologies, such as lithium ion batteries, will greatly facilitate the achievement of a global goal of carbon neutralization, further deferring the advent of the foreseeable energy crisis. The demand of lithium ion batteries is continuously increased, but the raw material resources are limited, so that the cost of the lithium ion batteries is increased suddenly. Sodium and lithium have similar physical and chemical properties, sodium resources are very abundant in crust, account for 2.74% of the element content of crust, and are distributed in various places worldwide without being limited by regions. Due to these characteristics of sodium, sodium ion batteries are ideal substitutes for lithium ion batteries, particularly with great advantages in large-scale energy storage applications.
With the continuous development of sodium ion batteries, more and more sodium ion full batteries are proposed, but are limited to button full batteries in laboratory environments, and few researches on sodium ion soft-pack batteries are reported. Therefore, the development and optimization of the pole piece preparation process and the cell assembly process of the sodium ion soft-package battery are of great significance to the commercial application of the sodium ion soft-package battery.
Disclosure of Invention
The invention aims to provide a water-based slurry polyanion type sodium ion soft-package battery and a preparation method thereof, which are used for solving the problems in the prior art.
In order to achieve the above object, the present invention provides the following solutions:
the invention provides a sodium ion soft-packed battery, wherein a polyanion type positive electrode material with a chemical formula of Na 3V2-x-ySbxTiyO(PO4)2F2 is adopted in a positive electrode plate of the sodium ion soft-packed battery, wherein x is more than 0 and less than or equal to 0.2, and y is more than 0 and less than or equal to 0.2.
The synergistic effect of the co-doping of the Ti and the Sb can improve the electron conductivity and the ion diffusion kinetics of the material, so that the rate performance and the cycle life of the positive electrode material are obviously improved.
As a further preferred aspect of the present invention, the positive electrode sheet is made of a polyanionic positive electrode material having a chemical formula of Na 3V1.88Sb0.03Ti0.09O(PO4)2F2 or Na 3V1.76Sb0.06Ti0.18O(PO4)2F2.
As a further preferable mode of the invention, the positive electrode plate is subjected to sodium pretreatment, and the positive electrode plate adopts water-based slurry as a binder.
As a further preferred aspect of the present invention, the aqueous slurry includes sodium carboxymethyl cellulose. More preferably a combination of sodium carboxymethylcellulose + styrene butadiene rubber.
As a further preferable mode of the invention, the negative electrode plate used for the sodium ion soft package battery contains a hard carbon negative electrode material.
As a further preferable aspect of the invention, the double-sided density of the positive electrode plate is 25-52mg/cm 2, and the double-sided density of the negative electrode plate is 10-20mg/cm 2.
The capacity of the sodium ion soft package battery prepared by the invention can reach 0.4-10Ah.
As a further preferred aspect of the present invention, the preparation method of the polyanionic cathode material having the chemical formula Na 3V2-x-ySbxTiyO(PO4)2F2 includes the steps of:
mixing vanadyl phosphate, vanadium phosphate, sodium fluoride, sodium carbonate, an antimony source and a titanium source, and calcining in a protective atmosphere to obtain the polyanion type positive electrode material with the chemical formula of Na 3V2-x-ySbxTiyO(PO4)2F2.
As a further preferred aspect of the present invention, the calcination temperature is 500-700 ℃ and the calcination time is 4-10 hours.
As a further preferred aspect of the present invention, the temperature rising rate is controlled to be 1-5 ℃ per minute when the calcination is performed, and the calcination is performed after reaching a temperature of 500-700 ℃.
As a further preferred aspect of the present invention, the molar ratio of the vanadyl phosphate, vanadium phosphate, sodium fluoride, sodium carbonate, antimony source and titanium source is 2-x-y:2-x-y:4:1:2x:2y, wherein 0< x.ltoreq.0.2, 0< y.ltoreq.0.2.
The vanadyl phosphate can be prepared by pulverizing and mixing vanadyl pentoxide and ammonium dihydrogen phosphate at a molar ratio of 1:2, fully mixing, sintering in air atmosphere at 700-800 ℃ for 2-6h to obtain the raw material VOPO 4.
The vanadium phosphate can be prepared by crushing and mixing vanadium pentoxide, ammonium dihydrogen phosphate and conductive carbon according to a molar ratio of 1:2:0.2, fully mixing, sintering in an argon atmosphere at 800-900 ℃ for 2-6h, and obtaining the raw material VPO 4.
As a further preferred aspect of the present invention, the antimony source comprises one or more of antimony trioxide, antimony pentoxide or antimony acetate, and the titanium source comprises titanium monoxide, titanium dioxide or titanium sesquioxide.
As a further preferred aspect of the present invention, the pre-sodium treatment includes a step of immersing the positive electrode sheet in a biphenyl-sodium solution or a naphthalene-sodium solution. More preferably, the concentration of the biphenyl-sodium solution or naphthalene-sodium solution is 0.1-2mol/L.
More specifically, the solvent of the pre-sodium solution used for pre-sodium treatment in the invention is an aprotic solvent, which comprises one of ethylene glycol dimethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran and tetrahydropyran, the solute is biphenyl or naphthalene and metallic sodium, and the concentration of the solution is 0.1-2mol/L. The preparation method of the pre-sodium solution comprises the steps of adding biphenyl or naphthalene into one solvent of ethylene glycol dimethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran and tetrahydropyran, stirring and dissolving, and then adding metal sodium to form a biphenyl-sodium or naphthalene-sodium solution.
The invention also provides a preparation method of the sodium ion soft package battery, which comprises the following steps:
and laminating the positive pole piece and the negative pole piece in a Z-shaped manner, adding electrolyte to package, and obtaining the sodium ion soft package battery.
More specifically, the sodium ion soft package battery comprises a positive electrode plate, a diaphragm, a negative electrode plate, electrolyte, a tab and an aluminum plastic film package.
As a further preferred mode of the invention, the preparation method of the positive electrode plate comprises the following steps of mixing polyanionic positive electrode material, super-P, sodium carboxymethyl cellulose and styrene-butadiene rubber according to the mass ratio of 91:5:2:2, coating the mixture on an aluminum foil in double sides, drying the mixture for 10-15 hours under the vacuum condition of 80-120 ℃ to obtain the positive electrode plate, rolling the positive electrode plate until the compaction density is 2.0-2.5g/cm 3, and die-cutting the positive electrode plate until the size is (55.2 mm-83 mm) (85.5 mm-163 mm) to obtain the positive electrode plate.
As a further preferred mode of the invention, the preparation method of the negative electrode plate comprises the following steps of mixing hard carbon negative electrode materials, super-P, styrene-butadiene rubber and sodium carboxymethyl cellulose according to the mass ratio of 92:3:2.5:2.5, then coating the mixture on an aluminum foil in a double-sided manner, drying the mixture for 10-15 hours by a 60-90 ℃ air drying box to obtain the hard carbon negative electrode plate, rolling the negative electrode plate to compact density of 1.0-1.5g/cm 3, and die-cutting the negative electrode plate to size (57.2-85 mm) of 87.0-165 mm to obtain the hard carbon negative electrode plate.
As a further preferable mode of the invention, when the pre-sodium treatment is carried out, the positive electrode plate is soaked in biphenyl-sodium solution or naphthalene-sodium solution for 0.05-2h, then one of ethylene glycol dimethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran and tetrahydropyran is used for cleaning 3 times, and vacuum drying is carried out for 8-12h at 60-90 ℃ to obtain the pre-sodium positive electrode plate.
As a further preferred aspect of the invention, during the preparation of the battery, the positive electrode plate has a compacted density of 2.0-2.5g/cm 3, a die-cut size of (55.2 mm-83 mm) (85.5 mm-163 mm), the negative electrode plate has a compacted density of 1.0-1.5 g/cm 3, and a die-cut size of (57.2 mm-85 mm) (87.0 mm-165 mm). The positive and negative pole pieces with higher compaction density can realize the assembly of the high-capacity soft package battery.
More preferably, the sodium ion soft package battery is obtained by laminating 1-25 pre-sodium positive pole pieces and 2-26 negative pole pieces in sequence in a Z-shaped mode, adding electrolyte and packaging.
As a further preferred aspect of the present invention, the electrolyte is one of 1M NaPF 6 [ diethanol dimethyl ether (G2) +vinylene carbonate (VC) ] [ V (G2): V (VC) =1:0.05 ] and 1M NaPF 6 [ Ethylene Carbonate (EC) +dimethyl carbonate (DMC) +methyl ethyl carbonate (EMC) ] [ V (EC): V (DMC): V (EMC) =1:1:1 ].
The invention discloses the following technical effects:
The invention adopts the polyanion type positive electrode material Na 3V2-x-ySbxTiyO(PO4)2F2 with high working voltage of 3.8V and good water stability as the positive electrode material of the sodium ion soft package battery, thereby ensuring the stability and energy density of the battery.
On the basis of adopting Na 3V2-x-ySbxTiyO(PO4)2F2 vanadium-based polyanion anode material, the invention can further adopt a water-based binder to manufacture the pole piece, thereby avoiding the use of toxic and high-cost N-methylpyrrolidone solvent.
The chemical pre-sodium treatment of the positive electrode plate can provide additional active sodium, compensates irreversible sodium loss of the soft-packed battery, such as capture of sodium ions by solid electrolyte interface film and negative electrode structural defects, and the like in the circulating process, and is beneficial to improving the circulating stability of the soft-packed battery.
The sodium ion soft-package battery has excellent multiplying power performance and long cycle life, and can be widely applied to the fields of large-scale energy storage, new energy automobiles and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the cycle performance of sodium ion soft pack batteries prepared in example 1 of the present invention and comparative example 1;
FIG. 2 is a graph showing the formation and first-turn charge/discharge curves of the sodium-ion soft pack battery prepared in example 1 of the present invention;
FIG. 3 is a graph (0.5C magnification) showing the cycle performance of sodium ion soft pack batteries prepared in example 1 of the present invention and comparative examples 3 and 4;
fig. 4 is a graph showing the formation and first-turn charge/discharge curves of the sodium ion soft pack battery prepared in example 2 of the present invention;
FIG. 5 is a graph showing the cycle performance (1C magnification) of the sodium ion soft pack battery prepared in example 2 of the present invention;
FIG. 6 is a graph showing the formation and first-turn charge/discharge curves of the sodium-ion soft pack battery prepared in example 3 of the present invention;
FIG. 7 is a graph showing the cycle performance (0.5C rate) of the sodium ion soft pack battery prepared in example 3 of the present invention;
FIG. 8 is a graph showing the formation and first-turn charge/discharge curves of the sodium-ion soft pack battery prepared in example 4 of the present invention;
fig. 9 is a cycle performance (0.1C rate) of the sodium ion soft pack battery prepared in example 4 of the present invention;
FIG. 10 is a schematic view of sodium ion soft pack battery prepared in examples 1-4 of the present invention;
FIG. 11 is a charge-discharge curve (1C magnification) of the water stability test of the positive electrode material prepared in example 1 of the present invention;
FIG. 12 is a cycle performance chart (1C magnification) of the water stability test of the positive electrode material prepared in example 1 of the present invention;
FIG. 13 is an SEM and Mapping elemental analysis chart of the cathode material synthesized in Experimental example 1 of the present invention;
Fig. 14 is an SEM and Mapping elemental analysis diagram of the cathode material synthesized in experimental example 2 of the present invention.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
Example 1
A preparation method of a polyanionic sodium ion soft package battery comprises the following steps:
(1) The preparation of the positive electrode plate comprises the steps of mixing an active material, conductive carbon, a binder 1 and a binder 2 according to the mass ratio of 91:5:2:2, namely weighing 455g of Na 3V1.88Sb0.03Ti0.09O(PO4)2F2 positive electrode material (active material), 25g of Super-P (conductive carbon), 10g of sodium carboxymethyl cellulose (binder 1) and 10g of styrene-butadiene rubber (binder 2), mixing, adjusting the viscosity of slurry to 6000 mPa.s by controlling the addition amount of deionized water, coating the slurry on an aluminum foil on both sides, and drying for 12 hours under the vacuum condition at 80 ℃, wherein the mass of the active material per unit area is approximately 25.64mg/cm 2. The preparation method of the Na 3V1.88Sb0.03Ti0.09O(PO4)2F2 positive electrode material comprises the steps of crushing and mixing vanadyl phosphate, vanadium phosphate, sodium fluoride, sodium carbonate, antimony trioxide, antimony acetate and titanium trioxide in a molar ratio of 0.95:0.95:2:0.5:0.05:0.05 (wherein the molar ratio of the antimony trioxide to the antimony acetate is 1:1) in a crusher, calcining in an argon atmosphere, wherein the sintering temperature is 600 ℃, the heating rate is 5 ℃ per minute, the sintering time is 6 hours, and obtaining the Na 3V1.88Sb0.03Ti0.09O(PO4)2F2 positive electrode material, wherein the synthesized material is proved to be an Sb and Ti co-doped positive electrode material through ICP characterization.
(2) The preparation of the negative electrode plate comprises the steps of weighing 460g of hard carbon negative electrode material (active material), 15g of Super-P (conductive carbon), 12.5g of sodium carboxymethyl cellulose (binder 1) and 12.5g of styrene-butadiene rubber (binder 2), adjusting the viscosity of slurry to 5000 mPa.s by controlling the addition amount of deionized water, coating the slurry on an aluminum foil in double sides, drying the slurry for 12 hours under the vacuum condition at 80 ℃, and controlling the mass of the active material per unit area to be about 12.39mg/cm 2.
(3) The positive pole piece and the negative pole piece are rolled, wherein a roll gap of 160 mu m is selected for rolling the positive pole piece so that the compacted density of the positive pole piece is 2.1g/cm 3, a roll gap of 130 mu m is selected for rolling the hard carbon negative pole piece so that the compacted density of the negative pole piece is 1.02g/cm 3, and the positive pole piece and the negative pole piece after rolling show mirror effects.
(4) The pole piece die cutting step comprises the steps of die cutting the positive pole piece to a positive pole piece with the width of 55.2mm, the length of 85.5mm, the length of the lug of 12mm and the width of 12mm, and die cutting the negative pole piece to a negative pole piece with the width of 57.2mm, the length of 87.0mm and the length of the lug of 12 mm.
(5) And pre-sodium the positive electrode, namely soaking 3 positive electrode plates in 1mol/L biphenyl-sodium solution for 1h under inert atmosphere, cleaning for 3 times by using ethylene glycol dimethyl ether solution, and vacuum drying at 80 ℃ for 12h to obtain the pre-sodium positive electrode plates.
(6) The sodium ion soft package battery is prepared by laminating 3 pre-sodium positive pole pieces, a celgard2500 diaphragm and 4 negative pole pieces in a Z-shaped sequence, fixing the positive pole pieces by using electrolyte-resistant adhesive tapes, and welding aluminum pole lugs and pole lug of the pole pieces together by using an ultrasonic spot welder. And (3) placing the battery core after the electrode lugs are welded into a semi-open aluminum plastic film for top and side sealing, transferring the battery core into a vacuum oven at 80 ℃ for drying for 6 hours, injecting electrolyte 1M NaPF 6 (ethylene carbonate (EC) +dimethyl carbonate (DMC) +methylethyl carbonate (EMC)) into the battery core after the drying is finished, and packaging to obtain the polyanion sodium ion soft package battery.
(7) And (3) forming the sodium ion soft package battery, namely placing the assembled soft package battery in a vacuum oven at 40 ℃ for standing for 12 hours, and then forming the battery on a blue charge-discharge tester, wherein the voltage range is 0.2-4.3V, and the forming conditions are that (1) 0.05C constant current is charged to 3.8V, (2) 0.1C constant current is charged to 4.3V, and (3) 0.1C constant current is discharged to 0.2V.
Sodium ion soft package battery test:
And (3) carrying out vacuum exhaust and pressurizing test on the formed sodium ion soft package battery, placing the two sealed batteries on a blue charge-discharge tester for electrochemical performance test, and circularly carrying out at 0.5C multiplying power, wherein 1 C=129 mA/g and the voltage range is 1.5-4.2V.
Fig. 2 is a graph showing the formation and 0.1C first-turn charge and discharge curves of the sodium ion soft pack battery prepared in example 1 of the present invention. Fig. 3 is a graph showing the 0.5C cycle performance of the sodium ion pouch cell prepared in example 1 of the present invention.
The sodium ion soft package battery designed in the embodiment 1 of the invention has the capacity of 0.5Ah, the first-cycle discharge capacity (0.1C) of 350mAh, the capacity retention rate of 100 cycles of 0.5C of 94.2% and the mass energy density of 95.2Wh/kg.
Example 2
A preparation method of a polyanionic sodium ion soft package battery comprises the following steps:
(1) The preparation of the positive electrode plate comprises the steps of mixing an active material, conductive carbon, a binder 1 and a binder 2 according to the mass ratio of 91:5:2:2, namely weighing 455g of Na 3V1.76Sb0.06Ti0.18O(PO4)2F2 positive electrode material (active material), 25g of Super-P (conductive carbon), 10g of sodium carboxymethyl cellulose (binder 1) and 10g of styrene-butadiene rubber (binder 2), mixing, adjusting the viscosity of slurry to 6000 mPa.s by controlling the addition amount of deionized water, coating the slurry on an aluminum foil on both sides, and drying for 12 hours under the vacuum condition at 80 ℃ and controlling the mass of the active material per unit area to be approximately 48.96mg/cm 2. The preparation method of the Na 3V1.76Sb0.06Ti0.18O(PO4)2F2 positive electrode material comprises the steps of crushing and mixing vanadyl phosphate, vanadium phosphate, sodium fluoride, sodium carbonate, antimony trioxide, antimony acetate and titanium trioxide in a molar ratio of 0.9:0.9:2:0.5:0.1:0.1 (wherein the molar ratio of the antimony trioxide to the antimony acetate is 1:1) in a crusher, calcining in an argon atmosphere, wherein the sintering temperature is 600 ℃, the heating rate is 5 ℃ per minute, the sintering time is 6 hours, and obtaining the Na 3V1.76Sb0.06Ti0.18O(PO4)2F2 positive electrode material, wherein the synthesized material is proved to be the Sb and Ti co-doped positive electrode material through ICP characterization.
(2) The preparation of the negative electrode plate comprises the steps of weighing 460g of hard carbon negative electrode material (active material), 15g of Super-P (conductive carbon), 12.5g of sodium carboxymethyl cellulose (binder 1) and 12.5g of styrene-butadiene rubber (binder 2), adjusting the viscosity of slurry to 5000 mPa.s by controlling the addition amount of deionized water, coating the slurry on an aluminum foil in double sides, drying the slurry for 12 hours under the vacuum condition of 80 ℃, and controlling the mass of the active material per unit area to be approximately 15.34mg/cm 2.
(3) The positive pole piece and the negative pole piece are rolled, wherein a roll gap of 160 mu m is selected for rolling the positive pole piece so that the compacted density of the positive pole piece is 2.2g/cm 3, a roll gap of 130 mu m is selected for rolling the hard carbon negative pole piece so that the compacted density of the negative pole piece is 1.05g/cm 3, and the positive pole piece and the negative pole piece after rolling show mirror effects.
(4) The pole piece die cutting step comprises the steps of die cutting the positive pole piece to a positive pole piece with the width of 55.2mm, the length of 85.5mm, the length of the lug of 12mm and the width of 12mm, and die cutting the negative pole piece to a negative pole piece with the width of 57.2mm, the length of 87.0mm and the length of the lug of 12 mm.
(5) And pre-sodium the positive electrode, namely soaking 4 positive electrode plates in 1mol/L biphenyl-sodium solution for 1h under inert atmosphere, cleaning for 3 times by using ethylene glycol dimethyl ether solution, and vacuum drying at 80 ℃ for 12h to obtain the pre-sodium positive electrode plate.
(6) The sodium ion soft package battery is prepared by laminating 4 pre-sodium positive pole pieces, a celgard2500 diaphragm and 5 negative pole pieces in a Z-shaped sequence, fixing the positive pole pieces by using electrolyte-resistant adhesive tapes, and welding aluminum pole lugs and pole lug of the pole pieces together by using an ultrasonic spot welder. And (3) placing the battery cell after welding the electrode lug into a semi-open aluminum plastic film for top and side sealing, transferring into a vacuum oven at 80 ℃ for drying for 6 hours, injecting electrolyte into the battery cell after the drying is finished, wherein the concentration of the electrolyte is 1mol/L, the solute is sodium hexafluorophosphate, the solvent is diethylene glycol dimethyl ether (G2), the additive is Vinylene Carbonate (VC), V (G2): V (VC) =1:0.05, and packaging to obtain the polyanion sodium ion soft package battery.
(7) And (3) forming the sodium ion soft package battery, namely placing the assembled soft package battery in a vacuum oven at 40 ℃ for standing for 12 hours, and then forming the battery on a blue charge-discharge tester, wherein the voltage range is 0.2-4.3V, and the forming conditions are that (1) 0.05C constant current is charged to 3.8V, (2) 0.1C constant current is charged to 4.3V, and (3) 0.1C constant current is discharged to 0.2V.
Sodium ion soft package battery test:
And (3) carrying out vacuum exhaust and pressurizing test on the formed sodium ion soft package battery, placing the two sealed batteries on a blue charge-discharge tester for electrochemical performance test, and circularly carrying out at 0.5C multiplying power, wherein 1 C=129 mA/g and the voltage range is 1.5-4.2V.
Fig. 4 is a first-turn charge-discharge curve of the sodium ion soft pack battery prepared in example 2 of the present invention. Fig. 5 is a cycle performance (1C magnification) of the sodium ion soft pack battery prepared in example 2 of the present invention.
The soft package battery designed in the embodiment 2 of the invention has the capacity of 1Ah, the initial ring capacity of 0.1C of 0.79Ah, the capacity retention rate of 85.7% after 500 circles of circulation under the 1C multiplying power, and the mass energy density of 114Wh/kg.
Example 3
A preparation method of a polyanionic sodium ion soft package battery comprises the following steps:
(1) The preparation of the positive electrode plate comprises the steps of mixing an active material, conductive carbon, a binder 1 and a binder 2 according to the mass ratio of 91:5:2:2, namely weighing 455g of Na 3V1.76Sb0.06Ti0.18O(PO4)2F2 positive electrode material (active material), 25g of Super-P (conductive carbon), 10g of sodium carboxymethyl cellulose (binder 1) and 10g of styrene-butadiene rubber (binder 2), mixing, adjusting the viscosity of slurry to 6000 mPa.s by controlling the addition amount of deionized water, coating the slurry on an aluminum foil on both sides, and drying for 12 hours under the vacuum condition at 80 ℃, wherein the mass of the active material per unit area is approximately 42.80mg/cm 2. The Na 3V1.76Sb0.06Ti0.18O(PO4)2F2 positive electrode material is prepared by crushing and mixing vanadyl phosphate, vanadium phosphate, sodium fluoride, sodium carbonate, antimony trioxide, antimony acetate and titanium trioxide according to the proportion of 0.9:0.9:2:0.5:0.1:0.1 (wherein the mol ratio of the antimony trioxide to the antimony acetate is 1:1) in a crusher, calcining in an argon atmosphere at the sintering temperature of 600 ℃, the heating rate of 5 ℃ per minute and the sintering time of 6 hours to obtain the Na 3V1.76Sb0.06Ti0.18O(PO4)2F2 positive electrode material, wherein the synthesized material is proved to be the Sb and Ti co-doped positive electrode material by ICP characterization.
(2) The preparation of the negative electrode plate comprises the steps of weighing 460g of hard carbon negative electrode material (active material), 15g of Super-P (conductive carbon), 12.5g of sodium carboxymethyl cellulose (binder 1) and 12.5g of styrene-butadiene rubber (binder 2), adjusting the viscosity of slurry to 5000 mPa.s by controlling the addition amount of deionized water, coating the slurry on an aluminum foil in double sides, drying the slurry for 12 hours under the vacuum condition of 80 ℃, and controlling the mass of the active material per unit area to be approximately 15.35mg/cm 2.
(3) The positive pole piece and the negative pole piece are rolled, wherein a roll gap of 160 mu m is selected for rolling the positive pole piece so that the compacted density of the positive pole piece is 2.2g/cm 3, a roll gap of 130 mu m is selected for rolling the hard carbon negative pole piece so that the compacted density of the negative pole piece is 1.05g/cm 3, and the positive pole piece and the negative pole piece after rolling show mirror effects.
(4) The pole piece die cutting step comprises the steps of die cutting the positive pole piece to a positive pole piece with the width of 55.2mm, the length of 85.5mm, the length of the lug of 12mm and the width of 12mm, and die cutting the negative pole piece to a negative pole piece with the width of 57.2mm, the length of 87.0mm and the length of the lug of 12 mm.
(5) And pre-sodium the positive electrode, namely soaking 10 positive electrode plates in 1mol/L biphenyl-sodium solution for 1h under inert atmosphere, cleaning for 3 times by using ethylene glycol dimethyl ether solution, and vacuum drying at 80 ℃ for 12h to obtain the pre-sodium positive electrode plates.
(6) The sodium ion soft package battery is prepared by laminating 10 pre-sodium positive pole pieces, a celgard2500 diaphragm and 11 negative pole pieces in a Z-shaped sequence, fixing the positive pole pieces by using electrolyte-resistant adhesive tapes, and welding aluminum pole lugs and pole lug of the pole pieces together by using an ultrasonic spot welder. And (3) placing the battery cell after welding the electrode lug into a semi-open aluminum plastic film for top and side sealing, transferring into a vacuum oven at 80 ℃ for drying for 6 hours, injecting electrolyte into the battery cell after the drying is finished, wherein the concentration of the electrolyte is 1mol/L, the solute is sodium hexafluorophosphate, the solvent is diethylene glycol dimethyl ether (G2), the additive is Vinylene Carbonate (VC), V (G2): V (VC) =1:0.05, and packaging to obtain the polyanion sodium ion soft package battery.
(7) And (3) forming the sodium ion soft package battery, namely placing the assembled soft package battery in a vacuum oven at 40 ℃ for standing for 12 hours, and then forming the battery on a blue charge-discharge tester, wherein the voltage range is 0.2-4.3V, and the forming conditions are that (1) 0.05C constant current is charged to 3.8V, (2) 0.1C constant current is charged to 4.3V, and (3) 0.1C constant current is discharged to 0.2V.
Sodium ion soft package battery test:
And (3) carrying out vacuum exhaust and pressurizing test on the formed sodium ion soft package battery, placing the two sealed batteries on a blue charge-discharge tester for electrochemical performance test, and circularly carrying out at 0.5C multiplying power, wherein 1 C=129 mA/g and the voltage range is 1.5-4.2V.
Fig. 6 is a graph showing the formation and first-turn charge and discharge curves of the sodium ion soft pack battery prepared in example 3 of the present invention. Fig. 7 is a cycle performance (0.5C rate) of the sodium ion pouch cell prepared in example 3 of the present invention.
The sodium ion soft package battery designed in the embodiment 3 of the invention has the capacity of 2Ah, the initial ring capacity of 0.1C of 1.86Ah and the capacity retention rate of 87.5% after 95 circles of circulation under the multiplying power of 0.5C, and the mass energy density of 131.2Wh/kg.
Example 4
A preparation method of a polyanionic sodium ion soft package battery comprises the following steps:
(1) The preparation of the positive electrode plate comprises the steps of mixing an active material, conductive carbon, a binder 1 and a binder 2 according to the mass ratio of 91:5:2:2, namely weighing 455g of Na 3V1.88Sb0.03Ti0.09O(PO4)2F2 positive electrode material (active material), 25g of Super-P (conductive carbon), 10g of sodium carboxymethyl cellulose (binder 1) and 10g of styrene-butadiene rubber (binder 2), mixing, adjusting the viscosity of slurry to 6000 mPa.s by controlling the addition amount of deionized water, coating the slurry on an aluminum foil on both sides, and drying for 12 hours under the vacuum condition at 80 ℃, wherein the mass of the active material per unit area is approximately 42.80mg/cm 2. The preparation method of the Na 3V1.88Sb0.03Ti0.09O(PO4)2F2 positive electrode material comprises the steps of crushing and mixing vanadyl phosphate, vanadium phosphate, sodium fluoride, sodium carbonate, antimony trioxide, antimony acetate and titanium trioxide in a molar ratio of 0.95:0.95:2:0.5:0.05:0.05 (wherein the molar ratio of the antimony trioxide to the antimony acetate is 1:1) in a crusher, calcining in an argon atmosphere, wherein the sintering temperature is 600 ℃, the heating rate is 5 ℃ per minute, the sintering time is 6 hours, and obtaining the Na 3V1.88Sb0.03Ti0.09O(PO4)2F2 positive electrode material, wherein the synthesized material is proved to be an Sb and Ti co-doped positive electrode material through ICP characterization.
(2) The preparation of the negative electrode plate comprises the steps of weighing 460g of hard carbon negative electrode material (active material), 15g of Super-P (conductive carbon), 12.5g of sodium carboxymethyl cellulose (binder 1) and 12.5g of styrene-butadiene rubber (binder 2), adjusting the viscosity of slurry to 5000 mPa.s by controlling the addition amount of deionized water, coating the slurry on an aluminum foil in double sides, drying the slurry for 12 hours under the vacuum condition of 80 ℃, and controlling the mass of the active material per unit area to be approximately 15.35mg/cm 2.
(3) The positive pole piece and the negative pole piece are rolled, wherein a roll gap of 160 mu m is selected for rolling the positive pole piece so that the compacted density of the positive pole piece is 2.2g/cm 3, a roll gap of 130 mu m is selected for rolling the hard carbon negative pole piece so that the compacted density of the negative pole piece is 1.05g/cm 3, and the positive pole piece and the negative pole piece after rolling show mirror effects.
(4) The pole piece die cutting step comprises the steps of die cutting the positive pole piece to a positive pole piece with the width of 83mm and the length of 163mm, the length of the lug of 12mm and the width of 12mm, and die cutting the negative pole piece to a negative pole piece with the width of 85mm and the length of 165mm and the length of the lug of 12 mm.
(5) And pre-sodium the positive electrode, namely soaking 18 positive electrode plates in 1mol/L biphenyl-sodium solution for 1h under inert atmosphere, cleaning for 3 times by using ethylene glycol dimethyl ether solution, and vacuum drying at 80 ℃ for 12h to obtain the pre-sodium positive electrode plates.
(6) The sodium ion soft package battery is prepared by laminating 18 pre-sodium positive pole pieces, a celgard2500 diaphragm and 19 negative pole pieces in a Z-shaped sequence, fixing the positive pole pieces by using electrolyte-resistant adhesive tapes, and welding aluminum pole lugs and pole lug of the pole pieces together by using an ultrasonic spot welder. And (3) placing the battery cell after welding the electrode lug into a semi-open aluminum plastic film for top and side sealing, transferring into a vacuum oven at 80 ℃ for drying for 6 hours, injecting electrolyte into the battery cell after the drying is finished, wherein the concentration of the electrolyte is 1mol/L, the solute is sodium hexafluorophosphate, the solvent is diethylene glycol dimethyl ether (G2), the additive is Vinylene Carbonate (VC), V (G2): V (VC) =1:0.05, and packaging to obtain the polyanion sodium ion soft package battery.
(7) And (3) forming the sodium ion soft package battery, namely placing the assembled soft package battery in a vacuum oven at 40 ℃ for standing for 12 hours, and then forming the battery on a blue charge-discharge tester, wherein the voltage range is 0.2-4.3V, and the forming conditions are that (1) 0.05C constant current is charged to 3.8V, (2) 0.1C constant current is charged to 4.3V, and (3) 0.1C constant current is discharged to 0.2V.
Sodium ion soft package battery test:
and (3) carrying out vacuum exhaust and pressurizing test on the formed sodium ion soft package battery, placing the two sealed batteries on a blue charge-discharge tester for electrochemical performance test, and circularly carrying out at 0.1C multiplying power, wherein 1 C=129 mA/g and the voltage range is 1.5-4.2V.
Fig. 8 is a graph showing the formation and first-turn charge and discharge curves of the sodium ion soft pack battery prepared in example 4 of the present invention. Fig. 9 is a cycle performance (0.1C rate) of the sodium ion pouch battery prepared in example 4 of the present invention.
The sodium ion soft package battery designed in the embodiment 4 of the invention has 10Ah capacity, 8.96Ah initial ring capacity of 0.1C and 88.5 percent of capacity retention rate after 20 circles of circulation under the multiplying power of 0.1C, and the mass energy density of the battery is 150Wh/kg.
Fig. 10 is a schematic diagram of sodium ion soft pack battery prepared in inventive examples 1 to 4.
Table i is inductively coupled plasma emission spectrometer test (ICP-OES) characterization data for the cathode materials synthesized in example 1 and example 2. As the volume of the Sb element is too large, the element molar ratio of Sb to Ti in the positive electrode material is 1:3, and the ICP result proves that the synthesized material is the Sb and Ti co-doped positive electrode material.
TABLE 1
Fig. 13 and 14 are Scanning Electron Microscope (SEM) and Mapping diagrams of the cathode materials synthesized in example 1 and example 2, respectively, and it can be seen that the cathode materials prepared in the invention all contain Na, O, F, P, V, sb, ti elements and are uniformly distributed, which proves that the synthesized materials are Sb and Ti co-doped cathode materials.
Table 2 shows the EDS spectrum analysis results of the cathode materials synthesized in example 1 and example 2, and it can be seen that the element ratios of the two cathode materials in example 1 and example 2 are substantially identical to the ICP results and the ratios in the molecular formulas.
TABLE 2
Comparative example 1
The difference from example 1 is only that the positive electrode sheet coating was performed by using an N-methylpyrrolidone slurry method. The preparation method of the positive electrode plate comprises the following steps of mixing conductive carbon and a binder according to the mass ratio of 91:5:4, namely weighing 455g of Na 3V1.88Sb0.03Ti0.09O(PO4)2F2 positive electrode material (active material), 25g gSuper-P (conductive carbon) and 20g of polyvinylidene fluoride (binder), adjusting the viscosity of the slurry to 6000 mPa.s by controlling the addition amount of N-methylpyrrolidone, and coating the slurry on an aluminum foil in double sides, wherein the rest steps are the same.
As shown in table 3, both the specific discharge capacity and the capacity retention rate of the aqueous slurry battery (example 1) at 1C rate were superior to those of the N-methylpyrrolidone slurry battery (comparative example 1).
TABLE 3 Table 3
Comparative example 2
In order to verify the effectiveness of the positive electrode sodium supplementing mode, the button half-cell assembly is performed, and performance verification is performed:
The positive electrode materials prepared in examples 1 to 4, conductive carbon black (Super-P), and sodium carboxymethyl cellulose (CMC) were mixed at a mass ratio of 7:2:1, and sufficiently dispersed with H 2 O as a solvent. Coating the prepared positive electrode slurry on an aluminum foil on one side, drying, punching, weighing, soaking the obtained positive electrode sheet in 1mol/L biphenyl-sodium solution for 10s under inert atmosphere, washing with ethylene glycol dimethyl ether solution for 3 times, vacuum drying at 80 ℃ for 12h to obtain a pre-sodium positive electrode sheet, then taking a metal sodium sheet as a negative electrode, wherein the concentration of electrolyte is 1mol/L, the solute is sodium perchlorate, the solvent is Ethylene Carbonate (EC) and Propylene Carbonate (PC), the additive is fluoroethylene carbonate (FEC), and V (EC) is V (PC) =1:1:0.1, thus assembling the CR2032 type button cell. The positive electrode material (prepared in example 1) without pretreatment was used as a control group, and the other steps were the same.
And performing charge and discharge tests on the blue battery test system. The voltage range is 2.0V-4.3V. The charge and discharge capacity and the first-turn coulombic efficiency of the obtained button cell were measured at 0.1C.
Performance versus table 4 shows that all pre-sodium positive pole pieces of examples 1-4 have a change in specific charge capacity, specific discharge capacity and coulombic efficiency at 0.1C rate compared to the non-pre-sodium positive pole piece (control), and the capacity retention rate is improved after 100 cycles of 1C rate.
TABLE 4 Table 4
Comparative example 3
The difference from example 1 is that the positive electrode material is doped with Sb element alone, i.e., the addition ratio of titanium sesquioxide is 0 in the positive electrode sheet preparation step, and the remaining steps are the same.
As shown in table 5, the rate performance of example 1 was significantly better than that of comparative example 3 doped with Sb element alone due to the synergistic effect of Ti and Sb co-doping. The capacity retention rate of 100 cycles at 0.5C in example 1 was 94.2% by the cycle performance test at 0.5C magnification, which is much higher than that of 81.6% in comparative example 3.
Comparative example 4
The difference from example 1 is that the positive electrode material is doped with Ti element alone, i.e., in the step of preparing the positive electrode sheet, the addition ratio of antimony trioxide and antimony acetate is 0, and the rest steps are the same.
As shown in table 5, the rate performance of example 1 was significantly better than that of comparative example 4 doped with Ti element alone due to the synergistic effect of Ti and Sb co-doping. The capacity retention rate of 100 cycles at 0.5C in example 1 was 94.2% higher than 92.3% of that in comparative example 4, by the cycle performance test at 0.5C magnification.
TABLE 5
Water stability test
The polyanionic cathode material synthesized in example 1 was placed in deionized water, stirred and soaked for 2 days, then assembled in a button half cell, and subjected to a cycle performance test at a 1C charge-discharge rate to test the cycle stability of the material.
FIG. 11 is a graph showing the 1C rate charge and discharge curve of a test material, wherein the 1C first-turn discharge capacity is 114.6 mAh.g -1, the fifty-turn discharge capacity is 112.3 mAh.g -1, and the first-hundred-turn discharge capacity is 109.7 mAh.g -1, and the material used in the invention has a high operating voltage of 3.8V.
Fig. 12 is a graph showing the 1C rate cycle performance of the test material, and the capacity retention rate of 95.1% after 100 cycles of charge and discharge, which proves that the polyanionic cathode material of the present invention has excellent water stability.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (6)
1. A sodium ion soft-package battery is characterized in that a polyanion type positive electrode material with a chemical formula of Na 3V1.88Sb0.03Ti0.09O(PO4)2F2 or Na 3V1.76Sb0.06Ti0.18O(PO4)2F2 is adopted in a positive electrode plate, the positive electrode plate is subjected to sodium pretreatment, and the positive electrode plate adopts water-based slurry as a binder;
The positive electrode plate is prepared by mixing the polyanion type positive electrode material, conductive carbon, a binder and deionized water to prepare slurry and coating the slurry on an aluminum foil;
the preparation method of the polyanionic positive electrode material with the chemical formula of Na 3V1.88Sb0.03Ti0.09O(PO4)2F2 or Na 3V1.76Sb0.06Ti0.18O(PO4)2F2 comprises the following steps:
Mixing vanadyl phosphate, vanadium phosphate, sodium fluoride, sodium carbonate, an antimony source and a titanium source, and calcining in a protective atmosphere to obtain the polyanion type positive electrode material with the chemical formula of Na 3V1.88Sb0.03Ti0.09O(PO4)2F2 or Na 3V1.76Sb0.06Ti0.18O(PO4)2F2;
When preparing the Na 3V1.88Sb0.03Ti0.09O(PO4)2F2 polyanionic cathode material, the molar ratio of the vanadyl phosphate, the vanadium phosphate, the sodium fluoride, the sodium carbonate, the antimony source and the titanium source is 1.88:1.88:4:1:0.06:0.18, and when preparing the Na 3V1.76Sb0.06Ti0.18O(PO4)2F2 polyanionic cathode material, the molar ratio of the vanadyl phosphate, the vanadium phosphate, the sodium fluoride, the sodium carbonate, the antimony source and the titanium source is 1.76:1.76:4:1:0.12:0.36.
2. The sodium ion pouch battery of claim 1, wherein the negative electrode sheet for the sodium ion pouch battery comprises a hard carbon negative electrode material.
3. The sodium ion pouch cell of claim 1, wherein the calcination temperature is 500-700 ℃ and the calcination time is 4-10 hours.
4. The sodium ion pouch cell of claim 1, wherein the antimony source comprises one or more of antimony trioxide, antimony pentoxide or antimony acetate and the titanium source comprises titanium monoxide, titanium dioxide or titanium dioxide.
5. The sodium ion pouch cell of claim 1, wherein the pre-sodium treatment comprises the step of immersing the positive electrode sheet in a biphenyl-sodium solution or a naphthalene-sodium solution.
6. The method for manufacturing a sodium ion pouch cell according to any one of claims 1 to 5, comprising the steps of:
And laminating the positive electrode plate and the negative electrode plate, adding electrolyte to package, and obtaining the sodium ion soft package battery.
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