CN115939405A - Calcium ion battery positive electrode active material and preparation method and application thereof - Google Patents
Calcium ion battery positive electrode active material and preparation method and application thereof Download PDFInfo
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- CN115939405A CN115939405A CN202310237414.5A CN202310237414A CN115939405A CN 115939405 A CN115939405 A CN 115939405A CN 202310237414 A CN202310237414 A CN 202310237414A CN 115939405 A CN115939405 A CN 115939405A
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910001424 calcium ion Inorganic materials 0.000 title claims abstract description 53
- 239000007774 positive electrode material Substances 0.000 title claims description 29
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000011734 sodium Substances 0.000 claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 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 abstract description 34
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 34
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 28
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 claims abstract description 22
- 125000005287 vanadyl group Chemical group 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 19
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000011149 active material Substances 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006467 substitution reaction Methods 0.000 claims abstract description 4
- 229940003871 calcium ion Drugs 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 16
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 16
- 239000010405 anode material Substances 0.000 claims description 9
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000011775 sodium fluoride Substances 0.000 claims description 8
- 235000013024 sodium fluoride Nutrition 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000002077 nanosphere Substances 0.000 claims description 3
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 claims description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 239000006183 anode active material Substances 0.000 abstract description 4
- CHQMXRZLCYKOFO-UHFFFAOYSA-H P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F Chemical compound P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F CHQMXRZLCYKOFO-UHFFFAOYSA-H 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000011575 calcium Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 206010021036 Hyponatraemia Diseases 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 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 class [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 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000012002 vanadium phosphate Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000002308 calcification Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 230000002441 reversible effect Effects 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Images
Classifications
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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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a calcium ion battery anode active material, a preparation method and an application thereof, wherein the calcium ion battery anode active material is vanadium sodium fluorophosphate NaV compounded with reduced graphene after electrochemical sodium removal 2 O 2 (PO 4 ) 2 F/rGO; the preparation method comprises the following steps: dissolving and mixing sodium salt, phosphorus source, fluorine source and vanadium sourceThen obtaining a mixed solution, and then adding the graphene dispersion liquid into the solution for ultrasonic treatment; transferring the mixed solution after ultrasonic treatment to a reaction kettle for hydrothermal reaction, and naturally cooling to room temperature after the reaction is finished to obtain a black product; centrifugally washing the black product, and freeze-drying to obtain the hollow nano spherical sodium vanadyl fluorophosphate Na compounded with the reduced graphene 3 V 2 O 2 (PO 4 ) 2 F/rGO; using topological substitution strategy to prepare sodium vanadyl fluorophosphate Na 3 V 2 O 2 (PO 4 ) 2 Removing two sodium ions in F/rGO to obtain sodium vanadyl fluorophosphate NaV 2 O 2 (PO 4 ) 2 F/rGO. The active material can improve the working voltage and the cycle life of the existing calcium ion battery.
Description
Technical Field
The invention belongs to the technical field of calcium ion battery anode materials, and particularly relates to a calcium ion battery anode active material, and a preparation method and application thereof.
Background
Lithium ion batteries are the latest technology used in portable electronic products, electric vehicles, and large-scale energy storage batteries, etc. However, the limited lithium resource (0.0017 wt%) and its uneven geographical distribution lead to higher costs for lithium and lithium-based alloys. In order to solve the current crisis, the polyvalent metal battery has attracted much attention in recent years due to its huge reserves and extremely high safety. In addition, the multi-electron process of the polyvalent metal is expected to further raise the limit of the energy density of the secondary battery, as compared with the monovalent ion battery. In contrast, the characteristics of the calcium ion battery are particularly outstanding. In a multivalent ion system, calcium has the lowest standard reduction potential (-2.87V vs standard hydrogen electrode) and polarization strength, and can realize higher output voltage, capacity and rate capability. The volumetric energy density of calcium metal is twice that of commercial graphite anodes. In addition, calcium is abundant in the earth's crust, and recent studies have shown that calcium metal is more prone to deposit in a dendrite-free form, and is more safe. Therefore, the development of a high-performance calcium ion battery system can greatly reduce the cost of an energy storage system and improve the use safety of the battery while relieving the shortage of lithium resources. In recent years, calcium metal negative electrodes and calcium electrolytes have been developed well, and positive electrode materials as important components of calcium ion batteries still face great challenges. The development of a positive electrode material having high capacity, high voltage and capable of operating at room temperature is an important direction for the research of future calcium ion batteries.
The polyanionic phosphate shows good application prospect in the anode material of the calcium battery due to the stable open three-position framework structure and high working voltage. Vanadium phosphates have a higher redox potential, higher thermal stability and low electrical conductivity than vanadium oxides or vanadates, due to the induction effect caused by the presence of the [ PO4] tetrahedra. Therefore, the improvement of the intrinsic ionic conductivity, the calcification degree, the working voltage and the structural stability of the vanadium phosphate has important significance for developing a high-energy density calcium ion battery with practical application value.
Disclosure of Invention
The invention provides a calcium ion battery anode active material, and aims to improve the working voltage and cycle life of the conventional calcium ion battery.
The invention also aims to provide a preparation method of the calcium ion battery positive electrode active material.
The invention also aims to provide the application of the calcium ion battery positive electrode material in the preparation of a calcium ion battery.
In order to achieve the purpose, the invention is realized by the following technical scheme:
on the one hand, the method provides a calcium ion battery positive active material, and the calcium ion battery positive active material is sodium vanadyl fluorophosphate NaV compounded with reduced graphene after electrochemical sodium removal 2 O 2 (PO 4 ) 2 F/rGO。
Preferably, the sodium vanadyl fluorophosphate NaV 2 O 2 (PO 4 ) 2 The shape of the F/rGO is a hollow nanosphere, and the diameter of the F/rGO is 50 to 100nm.
On the other hand, the invention provides a preparation method of the calcium ion battery positive electrode active material, which comprises the following steps:
(1) Dissolving and mixing a sodium salt, a phosphorus source, a fluorine source and a vanadium source to obtain a mixed solution, and then adding the graphene dispersion liquid into the solution for ultrasonic treatment;
(2) Transferring the mixed solution after ultrasonic treatment into a reaction kettle for hydrothermal reaction, and naturally cooling to room temperature after the reaction is finished to obtain a black product;
(3) Centrifugally washing the black product, and freeze-drying to obtain the hollow nano spherical sodium vanadyl fluorophosphate Na compounded with the reduced graphene 3 V 2 O 2 (PO 4 ) 2 F/rGO；
(4) Using topological substitution strategy to substitute sodium vanadyl fluorophosphate Na 3 V 2 O 2 (PO 4 ) 2 Removing two sodium ions in F/rGO to obtain sodium vanadyl fluorophosphate NaV 2 O 2 (PO 4 ) 2 F/rGO。
Preferably, in the step (1), the sodium salt is one or more of sodium fluoride, sodium acetate, sodium oxalate, sodium citrate, sodium hydroxide, sodium carbonate or sodium bicarbonate.
Preferably, the vanadium source is one or more of vanadium acetylacetonate, vanadyl acetylacetonate, ammonium metavanadate, vanadium pentoxide or vanadium trioxide.
Preferably, the phosphorus source is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphorus pentoxide or disodium hydrogen phosphate.
Preferably, the fluorine source is one or both of sodium fluoride or ammonium fluoride.
The solvent used for dissolving is different according to the solubility of the selected raw materials. Such as easily water-soluble substances, dissolved by water; such as a substance easily soluble in an organic solvent, is dissolved by an organic solvent (e.g., N-dimethylformamide, N-methylpyrrolidone, etc.).
Preferably, in the step (1), the dissolving process is carried out at 20-80 ℃.
Preferably, in the step (1), the solid-to-liquid ratio of the graphene dispersion liquid is (1-10): 1000.
Further preferably, the graphene in the graphene dispersion liquid is prepared by a Hummers method and then dispersed in water or DMF to obtain the graphene dispersion liquid.
Preferably, in step (2), the hydrothermal reaction parameters are: the temperature is 160 to 200 ℃, and the time is 20 to 30h.
Further preferably, in the step (2), the hydrothermal reaction parameters are: the temperature was 180 ℃ and the time was 24 hours.
Preferably, in step (3), the freeze-drying parameters are: the temperature is-40 to 60 ℃, and the time is 24 to 48h.
Preferably, in the step (3), deionized water and absolute ethyl alcohol are adopted for centrifugal washing for more than 1 time.
Preferably, in step (4), the strategy of topological substitution is as follows: sodium vanadyl fluorophosphate Na 3 V 2 O 2 (PO 4 ) 2 F/rGO serving as a positive electrode active material is assembled into a sodium ion battery, and then the sodium ion battery is discharged to 4-5V to obtain sodium vanadyl fluorophosphate NaV 2 O 2 (PO 4 ) 2 F/rGO. Further preferably, the discharge voltage is 4.5V.
In still another aspect, the invention provides an application of the calcium ion battery positive active material, wherein the sodium vanadyl fluorophosphate NaV 2 O 2 (PO 4 ) 2 The F/rGO is applied to the calcium ion battery as the positive electrode active material of the calcium ion battery.
Preferably, the calcium ion battery positive electrode material is obtained by grinding and mixing an active material and a conductive material, coating the mixture on the surface of a current collector material and then drying the mixture; the calcium ion battery positive electrode material is formed by mixing 60-80% of active material, 10-30% of conductive agent and 10% of binder by mass percentage; the active material is sodium vanadyl fluorophosphate NaV 2 O 2 (PO 4 ) 2 F/rGO。
Preferably, the current collector material is copper, aluminum, titanium or carbon paper; the conductive agent is conductive carbon black, acetylene black, carbon nano tubes, ketjen black or activated carbon; the binder is polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl alcohol, sodium carboxymethylcellulose or styrene butadiene rubber.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention is different from other calcium ion battery anode materials at present in the main active material. According to the invention, in the one-step hydrothermal synthesis process, graphene is introduced, so that the defect of poor conductivity of a polyanion salt material is overcome, the growth of material crystals is limited, the particle size of the nano material is limited below 100nm, and the ion diffusion capacity of the obtained material is enhanced.
(2) NaV obtained by electrochemical sodium removal 2 O 2 (PO 4 ) 2 F/rGO provides more active sites for calcium ion intercalation.
(3) The NaV of the invention 2 O 2 (PO 4 ) 2 The F/rGO positive electrode material is assembled into a battery, has good electrochemical performance, shows higher working voltage and longer cycle life, and has good comprehensive electrochemical performance. In addition, the synthesis process is simple, low in cost and beneficial to future commercial use.
Drawings
FIG. 1 shows Na obtained in example 1 of the present invention 3 V 2 O 2 (PO 4 ) 2 X-ray diffraction pattern of F/rGO;
FIG. 2 shows Na obtained in example 1 of the present invention 3 V 2 O 2 (PO 4 ) 2 SEM image of F/rGO;
FIG. 3 shows NaV obtained in example 1 of the present invention 2 O 2 (PO 4 ) 2 X-ray diffraction pattern of F/rGO;
FIG. 4 shows Na in example 1 of the present invention 3 V 2 O 2 (PO 4 ) 2 F/rGO serving as the anode of the sodium ion battery at the current density of 50 mA g -1 The sodium depletion curve below;
FIG. 5 shows the current density of 20 mA g for the calcium ion battery anode material of example 1 -1 A first circle charge-discharge curve in a lower neutralization potential interval of-0.5-1.5V;
FIG. 6 shows the current density of 20 mA g for the calcium ion battery anode material of the embodiment 1 -1 Lower and potential interval-cycle capacity and coulombic efficiency profiles obtained at 0.5-1.5V;
FIG. 7 shows the current density of 100 mA g for the calcium-ion battery cathode material of the embodiment 1 -1 The cycle capacity and the coulomb efficiency curve chart obtained in the lower and potential interval of-0.5-1.5V.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with the specific examples, but the present invention should not be construed as being limited thereto, and only by way of example.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are conventionally obtained commercially or prepared by conventional methods.
Example 1
1g of graphene powder prepared by the Hummers method is added into 100mL of DMF, and the mixture is subjected to ultrasonic treatment for 24 hours to obtain a graphene DMF phase dispersion liquid.
Dissolving 4.5 mmol sodium fluoride and 3mmol ammonium dihydrogen phosphate in 15 mL water to obtain solution A3 mmol vanadyl acetylacetonate was dissolved in 10 mL DMF to form solution B, which was slowly poured into solution B and stirred for 20 minutes to obtain solution C.
5mL of graphene oxide DMF phase dispersion is added into the solution C, and ultrasonic treatment is carried out for 1 hour.
And sealing the solution in a reaction kettle, placing the reaction kettle in an oven, carrying out hydrothermal reaction for 24 hours at 180 ℃, and naturally cooling to room temperature after the reaction is finished to obtain a black product. Washing the obtained product with water and ethanol repeatedly several times, and freeze-drying at-50 deg.C for 24 hr to obtain product Na 3 V 2 O 2 (PO 4 ) 2 F/rGO。
Mixing the obtained Na 3 V 2 O 2 (PO 4 ) 2 Preparing electrode slurry by using F/rGO, acetylene black and PVDF (NMP as a solvent) according to the proportion of 7 3 V 2 (PO 4 ) 2 O 2 F/rGO electrode sheet.The electrode sheet is used as a positive electrode, metal sodium is used as a negative electrode, and 1M NaClO 4 (EC: DMC =1 Vol% plus 5% FEC solution as solvent) as electrolyte, whatman glass fiber as battery diaphragm, assembling into sodium ion button battery.
The cell was charged at 50 mA g -1 Charging to 4.5V at the current density of the NaV to obtain the NaV 2 O 2 (PO 4 ) 2 F/rGO。
Mixing NaV 2 O 2 (PO 4 ) 2 F/rGO as anode, activated Carbon Cloth (ACC) as cathode, 0.8M Ca (TFSI) 2 And (EC: DMC: PC: EMC =1 Vol% as solvent) as electrolyte and Whatman glass fiber as battery diaphragm to assemble the calcium ion button battery.
Example 2
Adding 1g of graphene powder prepared by the Hummers method into 500mL of DMF, and performing ultrasonic treatment for 24 hours to obtain a graphene DMF phase dispersion liquid.
2mmol of NH 4 H 2 PO 4 、2mmol NH 4 VO 3 1mmol NaF and 1mmol Na 2 CO 3 Dissolved in 5mL of deionized water, respectively.
The above 4 solutions were all added to 25mL of a graphene oxide DMF phase dispersion, and stirred at 90 ℃ for 30 minutes.
And sealing the solution in a reaction kettle, placing the reaction kettle in an oven, carrying out hydrothermal reaction for 24 hours at 180 ℃, and naturally cooling to room temperature after the reaction is finished to obtain a black product. Washing the obtained product with water and ethanol repeatedly for several times, and freeze-drying at-50 deg.C for 24 hr to obtain product Na 3 V 2 O 2 (PO 4 ) 2 F/rGO。
Mixing the obtained Na 3 V 2 O 2 (PO 4 ) 2 Preparing electrode slurry by using F/rGO, acetylene black and PVDF (NMP as a solvent) according to the proportion of 7 3 V 2 (PO 4 ) 2 O 2 F/rGO electrode sheet. The electrode sheet is used as a positive electrode, metal sodium is used as a negative electrode, and 1M NaClO 4 (EC: DMC = 1% 1 Vol plus 5% FEC solution as solvent) as a solventAnd electrolyte and Whatman glass fiber are used as a battery diaphragm to assemble the sodium-ion battery.
The cell was charged at 50 mA g -1 Charging to 4.5V at the current density of the NaV to obtain the NaV 2 O 2 (PO 4 ) 2 F/rGO。
Mixing NaV 2 O 2 (PO 4 ) 2 F/rGO as anode, activated carbon cloth as cathode, 0.8M Ca (TFSI) 2 And (EC: DMC: PC: EMC =1 Vol% as solvent) as electrolyte and Whatman glass fiber as battery diaphragm to assemble the calcium ion button battery.
Example 3
Adding 1g of graphene powder prepared by the Hummers method into 500mL of deionized water, and performing ultrasonic treatment for 24 hours to obtain the graphene aqueous phase dispersion liquid.
2mmol of NH 4 H 2 PO 4 、2mmol NH 4 VO 3 3mmol of NaF were dissolved in 150mL of deionized water, respectively.
25mL of aqueous graphene dispersion was added to the above solution.
The above solution was used for the preparation of Na by spray drying 3 V 2 O 2 (PO 4 ) 2 F/rGO precursor. The atomization was controlled at an air pressure of 0.1 MPa and an inlet air temperature of 180 ℃.
Na is mixed with 3 V 2 O 2 (PO 4 ) 2 And heating the F/rGO precursor to 500 ℃ in a protective atmosphere, and keeping the temperature for 5 hours.
The obtained Na is added 3 V 2 O 2 (PO 4 ) 2 Preparing electrode slurry by using F/rGO, acetylene black and PVDF (NMP as a solvent) according to the proportion of 7 3 V 2 (PO 4 ) 2 O 2 F/rGO electrode sheet. The electrode sheet is used as a positive electrode, metal sodium is used as a negative electrode, and 1M NaClO 4 (EC: DMC = 1.
The cell was charged at 50 mA g -1 Current density of (4)5V, obtaining NaV 2 O 2 (PO 4 ) 2 F/rGO。
Mixing NaV 2 O 2 (PO 4 ) 2 F/rGO as anode, activated carbon cloth as cathode, 0.8M Ca (TFSI) 2 And (EC: DMC: PC: EMC =1 Vol% as solvent) as electrolyte and Whatman glass fiber as battery diaphragm to assemble the calcium ion button battery.
Example 4
Adding 1g of graphene powder prepared by the Hummers method into 500mL of DMF, and performing ultrasonic treatment for 24 hours to obtain a graphene DMF phase dispersion liquid.
Dissolving 2mmol vanadyl acetylacetonate in 60mL of a mixed solution of deionized water and ethanol (the volume ratio of water to ethanol is 1:1)
2mmol of NH 4 H 2 PO 4 And 3mmol NaF were added to the above solution.
Add 25mL of graphene DMF phase dispersion to the above solution and sonicate for 10 min.
And sealing the solution in a reaction kettle, placing the reaction kettle in an oven, carrying out hydrothermal reaction at 180 ℃ for 24 hours, and naturally cooling to room temperature after the reaction is finished to obtain a black product. The resulting product was washed with water and ethanol repeatedly several times and then dried in a vacuum oven at 120 ℃ for 8 hours to obtain product Na 3 V 2 O 2 (PO 4 ) 2 F/rGO。
Mixing the obtained Na 3 V 2 O 2 (PO 4 ) 2 Preparing electrode slurry by using F/rGO, acetylene black and PVDF (NMP as a solvent) according to the proportion of 7 3 V 2 O 2 (PO 4 ) 2 F/rGO electrode sheet. The electrode sheet is used as a positive electrode, metal sodium is used as a negative electrode, and 1M NaClO 4 (EC: DMC = 1.
The cell was charged at 50 mA g -1 Charging to 4.5V at the current density of the NaV to obtain the NaV 2 O 2 (PO 4 ) 2 F/rGO。
Mixing NaV 2 O 2 (PO 4 ) 2 F/rGO as anode, activated carbon cloth as cathode, 0.8M Ca (TFSI) 2 And (EC: DMC: PC: EMC =1 Vol% as solvent) as electrolyte and Whatman glass fiber as battery diaphragm to assemble the calcium ion button battery.
Sample characterization and Performance testing
(1) Sample characterization
FIG. 1 shows, na obtained 3 V 2 O 2 (PO 4 ) 2 The F/rGO shows high crystallinity without any impurities and all diffraction peaks can be well indexed as a tetragonal unit cell with an I4/mmm space group. Na (Na) 3 V 2 O 2 (PO 4 ) 2 The crystal structure of the F/rGO is a v octahedron and p tetrahedron roof-sharing connection, a pseudo-layered structure parallel to an ab surface is constructed, sodium ions are located in a cavity along the ab surface, the sodium ions have two different crystallization sites, namely a sodium 1 site and a sodium 2 site, and only the sodium ions of the sodium 1 site can be subjected to reversible intercalation and deintercalation. This arrangement allows the formation of wide channels within the polyanionic framework, facilitating the migration of ions.
FIG. 2 shows Na obtained in example 1 of the present invention 3 V 2 O 2 (PO 4 ) 2 SEM image of F/rGO shows that the morphology is hollow nanospheres with diameters of 50-100 nm.
FIG. 3 shows the NaV obtained in example 1 of the present invention after sodium removal 2 O 2 (PO 4 ) 2 X-ray diffraction pattern of F/rGO, the results show that Na is completely discharged 3 V 2 O 2 (PO 4 ) 2 F/rGO still keeps a tetragonal phase, and the space group is I4/mmm, thereby proving the structural stability.
(2) Performance testing
FIG. 4 shows NaV of example 1 of the present invention 2 O 2 (PO 4 ) 2 F/rGO serving as the anode of the sodium ion battery at the current density of 50 mA g -1 The sodium depletion curve below, showing two charging plateaus, further demonstrates the depletion of two sodium ions.
FIG. 5 shows the current density of the positive electrode material of the calcium-ion battery of example 1 of the present invention20 mA g -1 The first circle of charge-discharge curve under-0.5-1.5V of lower neutralization potential interval. As can be seen, the specific capacity of the first discharge cycle is as high as 103.6 mAh g -1 The average working voltage reaches 3.7V vs. Ca 2+ /Ca。
FIG. 6 shows the current density of 20 mA g for the anode material of calcium ion battery in example 1 of the present invention -1 The cycle capacity and the coulombic efficiency curve chart are obtained under the condition that the potential range is between-0.5 and 1.5V. As can be seen from the figure, the discharge specific capacity can be stabilized at 93.4 mAh g after the rapid attenuation of the first 10 circles and the activation cycle of 400 circles -1 The capacity retention rate exceeds 90%.
FIG. 7 shows the current density of 100 mA g for the anode material of calcium ion battery in example 1 of the present invention -1 The cycle capacity and the coulombic efficiency curve chart are obtained under the condition that the potential range is between-0.5 and 1.5V. As can be seen from the figure, the specific discharge capacity of the battery after 3000 cycles is 57.8 mAh g -1 The capacity retention rate is 62.3%, and the coulombic efficiency exceeds 98%.
According to the invention, the graphene and the polyanion salt sodium vanadyl fluorophosphate are effectively compounded together, the conductivity of the material is improved, and Na is added 3 V 2 O 2 (PO 4 ) 2 After two sodium ions are electrochemically removed from the F/rGO, the F/rGO is used as a calcium ion battery anode material for the first time, and the calcium ions can be reversibly inserted and removed and show excellent calcium storage performance. The method is simple, has low cost and can be used for large-scale production.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and it is obvious to those skilled in the art that the present invention is not limited to the details of the above-mentioned exemplary embodiments, and that the present invention can be embodied in any other specific form without departing from the spirit or essential characteristics thereof. Thus, the present embodiments are merely exemplary and non-limiting. The scope of the invention is indicated by the appended claims rather than the foregoing description, and all changes that come within the meaning and range of equivalency of the claims are intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. The calcium ion battery positive electrode active material is characterized by being sodium vanadyl fluorophosphate NaV compounded with reduced graphene after electrochemical sodium removal 2 O 2 (PO 4 ) 2 F/rGO。
2. The calcium-ion battery positive electrode active material according to claim 1, characterized in that: the sodium vanadyl fluorophosphate NaV 2 O 2 (PO 4 ) 2 The shape of the F/rGO is a hollow nanosphere, and the diameter of the F/rGO is 50 to 100nm.
3. A method for preparing the positive active material of the calcium-ion battery as claimed in any one of claims 1~2, comprising the steps of:
(1) Dissolving and mixing sodium salt, a phosphorus source, a fluorine source and a vanadium source to obtain a mixed solution, and then adding the graphene dispersion liquid into the solution for ultrasonic treatment;
(2) Transferring the mixed solution after ultrasonic treatment to a reaction kettle for hydrothermal reaction, and naturally cooling to room temperature after the reaction is finished to obtain a black product;
(3) Centrifugally washing the black product, and freeze-drying to obtain the hollow nano spherical sodium vanadyl fluorophosphate Na compounded with the reduced graphene 3 V 2 O 2 (PO 4 ) 2 F/rGO；
(4) Using topological substitution strategy to prepare sodium vanadyl fluorophosphate Na 3 V 2 O 2 (PO 4 ) 2 Two sodium ions in F/rGO are separated to obtain sodium vanadyl fluorophosphate NaV 2 O 2 (PO 4 ) 2 F/rGO。
4. The method for preparing a positive electrode active material for a calcium-ion battery according to claim 3, characterized in that: in the step (1), the sodium salt is one or more of sodium fluoride, sodium acetate, sodium oxalate, sodium citrate, sodium hydroxide, sodium carbonate or sodium bicarbonate; the vanadium source is one or more of vanadium acetylacetonate, vanadyl acetylacetonate, ammonium metavanadate, vanadium pentoxide or vanadium trioxide; the phosphorus source is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphorus pentoxide or disodium hydrogen phosphate; the fluorine source is one or two of sodium fluoride or ammonium fluoride.
5. The method for preparing a positive electrode active material for a calcium-ion battery according to claim 3, characterized in that: in the step (1), the solid-to-liquid ratio of the graphene dispersion liquid is (1-10): 1000.
6. The method for preparing a positive electrode active material for a calcium-ion battery according to claim 3, characterized in that: in the step (2), the hydrothermal reaction parameters are as follows: the temperature is 160 to 200 ℃, and the time is 20 to 30h; in the step (3), the freeze-drying parameters are as follows: the temperature is-40 to 60 ℃, and the time is 24 to 48h.
7. The method for preparing a positive electrode active material for a calcium-ion battery according to claim 3, characterized in that: in the step (4), the topology replacement strategy is as follows: sodium vanadyl fluorophosphate Na 3 V 2 O 2 (PO 4 ) 2 F/rGO serving as a positive electrode active material is assembled into a sodium ion battery, and then the sodium ion battery is discharged to 4-5V to obtain sodium vanadyl fluorophosphate NaV 2 O 2 (PO 4 ) 2 F/rGO。
8. Use of the positive active material of calcium ion battery of any of claims 1~2 wherein: the sodium vanadyl fluorophosphate NaV 2 O 2 (PO 4 ) 2 The F/rGO is applied to the calcium ion battery as the positive electrode active material of the calcium ion battery.
9. The use of the positive active material for a calcium-ion battery according to claim 8, wherein: the calcium ion battery anode material is prepared by grinding and mixing an active material and a conductive material, coating the mixture on the surface of a current collector material and then dryingDrying to obtain; the calcium ion battery positive electrode material is formed by mixing 60-80% of active material, 10-30% of conductive agent and 10% of binder by mass percentage; the active material is sodium vanadyl fluorophosphate NaV 2 O 2 (PO 4 ) 2 F/rGO。
10. The use of the positive electrode active material for a calcium-ion battery according to claim 9, wherein: the current collector is made of copper, aluminum, titanium or carbon paper; the conductive agent is conductive carbon black, acetylene black, carbon nano tubes, ketjen black or activated carbon; the binder is polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl alcohol, sodium carboxymethylcellulose or styrene butadiene rubber.
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