CN109196701A - A kind of Magnesium ion battery and preparation method thereof - Google Patents
A kind of Magnesium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN109196701A CN109196701A CN201680085081.7A CN201680085081A CN109196701A CN 109196701 A CN109196701 A CN 109196701A CN 201680085081 A CN201680085081 A CN 201680085081A CN 109196701 A CN109196701 A CN 109196701A
- Authority
- CN
- China
- Prior art keywords
- magnesium
- metal
- battery
- electrolyte
- anode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910001425 magnesium ion Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 59
- 239000011777 magnesium Substances 0.000 claims abstract description 37
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 29
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000007774 positive electrode material Substances 0.000 claims abstract description 22
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 19
- 239000002905 metal composite material Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- 239000006183 anode active material Substances 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000004020 conductor Substances 0.000 claims description 14
- 238000004513 sizing Methods 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 238000004381 surface treatment Methods 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000006258 conductive agent Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 229920006254 polymer film Polymers 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 239000011135 tin Substances 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 5
- 230000002441 reversible effect Effects 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical group 0.000 claims description 4
- 150000001412 amines Chemical group 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052790 beryllium Inorganic materials 0.000 claims description 4
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- 239000002608 ionic liquid Substances 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 150000003053 piperidines Chemical class 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 150000003457 sulfones Chemical class 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 238000009831 deintercalation Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000003487 electrochemical reaction Methods 0.000 abstract description 3
- 230000005611 electricity Effects 0.000 abstract 1
- 239000008151 electrolyte solution Substances 0.000 abstract 1
- -1 Mgx1MoO3 Chemical compound 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 239000005030 aluminium foil Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 9
- 238000009736 wetting Methods 0.000 description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- IFRDBGYJSLDMHQ-UHFFFAOYSA-J magnesium;disodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;hydrate Chemical compound O.[Na+].[Na+].[Mg+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O IFRDBGYJSLDMHQ-UHFFFAOYSA-J 0.000 description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 6
- 229910001623 magnesium bromide Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- ALTVCFKRYOLNPF-UHFFFAOYSA-N imino(trifluoromethyl)sulfanium Chemical class FC(F)(F)[S+]=N ALTVCFKRYOLNPF-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- RQWLNIIZFOLYGM-UHFFFAOYSA-M [NH2-].[Mg+]Cl Chemical compound [NH2-].[Mg+]Cl RQWLNIIZFOLYGM-UHFFFAOYSA-M 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 2
- LGCNDZIFJKHQHB-UHFFFAOYSA-N 1,3-dioxacycloundecan-2-one Chemical compound O=C1OCCCCCCCCO1 LGCNDZIFJKHQHB-UHFFFAOYSA-N 0.000 description 2
- 125000006091 1,3-dioxolane group Chemical class 0.000 description 2
- HSXKFFPORAOYHS-UHFFFAOYSA-N 1-butylpiperidine imino-bis(trifluoromethyl)-lambda4-sulfane Chemical compound FC(F)(F)S(=N)C(F)(F)F.C(CCC)N1CCCCC1 HSXKFFPORAOYHS-UHFFFAOYSA-N 0.000 description 2
- JRZSHQGHXPLFHX-UHFFFAOYSA-N 1-ethyl-3-methyl-2H-imidazole imino-bis(trifluoromethyl)-lambda4-sulfane Chemical compound FC(F)(F)S(=N)C(F)(F)F.C(C)N1CN(C=C1)C JRZSHQGHXPLFHX-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical class CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- SGSODRUBEXHGRA-UHFFFAOYSA-N FC(F)(F)S(=N)C(F)(F)F.C(CC)N1CN(C=C1)C Chemical compound FC(F)(F)S(=N)C(F)(F)F.C(CC)N1CN(C=C1)C SGSODRUBEXHGRA-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- 229910019393 Mg(BF4)2 Inorganic materials 0.000 description 2
- 229910019389 Mg(CF3SO3)2 Inorganic materials 0.000 description 2
- 229910019436 Mg(PF6)2 Inorganic materials 0.000 description 2
- 229910015463 Mo3S4 Inorganic materials 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- DUBJMEWQSPHFGK-UHFFFAOYSA-N [Mg].[V] Chemical compound [Mg].[V] DUBJMEWQSPHFGK-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical group CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 2
- NVJBFARDFTXOTO-UHFFFAOYSA-N diethyl sulfite Chemical group CCOS(=O)OCC NVJBFARDFTXOTO-UHFFFAOYSA-N 0.000 description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 2
- 229910001641 magnesium iodide Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- CVFYRFVPQPTBIB-UHFFFAOYSA-L magnesium;n-methylaniline;dibromide Chemical compound [Mg+2].[Br-].[Br-].CNC1=CC=CC=C1 CVFYRFVPQPTBIB-UHFFFAOYSA-L 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- YCCPTBSIWCOONA-UHFFFAOYSA-N prop-1-ene;sulfurous acid Chemical group CC=C.OS(O)=O YCCPTBSIWCOONA-UHFFFAOYSA-N 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- DTMHTVJOHYTUHE-UHFFFAOYSA-N thiocyanogen Chemical compound N#CSSC#N DTMHTVJOHYTUHE-UHFFFAOYSA-N 0.000 description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 2
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- BHSXLOMVDSFFHO-UHFFFAOYSA-N (3-ethylsulfanylphenyl)methanamine Chemical compound CCSC1=CC=CC(CN)=C1 BHSXLOMVDSFFHO-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- WZCSFLDGNKKODA-UHFFFAOYSA-H magnesium titanium(4+) diphosphate Chemical compound P(=O)([O-])([O-])[O-].[Mg+2].[Ti+4].P(=O)([O-])([O-])[O-] WZCSFLDGNKKODA-UHFFFAOYSA-H 0.000 description 1
- BYHVSMPVCOAEEA-UHFFFAOYSA-K magnesium;cobalt(2+);phosphate Chemical compound [Mg+2].[Co+2].[O-]P([O-])([O-])=O BYHVSMPVCOAEEA-UHFFFAOYSA-K 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910006400 μ-Cl Inorganic materials 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/399—Cells with molten salts
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
发明提供了一种镁离子电池及其制备方法，包括电池负极、电解液、隔膜和电池正极；其中，所述电池正极包括正极集流体和正极活性材料层，所述正极活性材料层包括正极活性材料，所述正极活性材料层包括自由可逆脱嵌镁离子的正极活性材料；所述电解液包括电解质和溶剂，所述电解质为镁盐；所述电池负极包括金属、金属合金或金属复合物导电材料中的一种或几种。本发明提供了一种镁离子电池，用镁替换锂，解决了锂资源储量有限的问题；节省了一个部件的体积和重量，能够降低电池的重量和体积，提高电池能量密度；且所发生的电化学反应的反应主体为镁离子，镁离子带有两个电荷，提高了电池的容量。
The invention provides a magnesium ion battery and a preparation method thereof, including a battery negative electrode, an electrolyte, a separator and a battery positive electrode; wherein, the battery positive electrode includes a positive electrode current collector and a positive electrode active material layer, and the positive electrode active material layer includes a positive electrode active material layer. material, the positive electrode active material layer includes a positive electrode active material that freely and reversibly deintercalates magnesium ions; the electrolyte solution includes an electrolyte and a solvent, and the electrolyte is a magnesium salt; the battery negative electrode includes a metal, a metal alloy or a metal composite to conduct electricity one or more of the materials. The invention provides a magnesium ion battery, which replaces lithium with magnesium, which solves the problem of limited lithium resource reserves; saves the volume and weight of a component, can reduce the weight and volume of the battery, and improves the energy density of the battery; The reaction main body of the electrochemical reaction is magnesium ion, and the magnesium ion has two electric charges, which improves the capacity of the battery.
Description
The present invention relates to field of batteries, in particular to a kind of Magnesium ion battery and preparation method thereof.
In today that new energy technology and application become more and more important, lithium ion battery becomes the first choice of current electronic product power source since specific capacity is high, energy density is high, have extended cycle life, cost performance is high and obtains extensive concern and application.The core building block of lithium ion battery generally comprises anode, cathode and electrolyte.Commercial lithium ion battery is mainly using transition metal oxide or polyanionic metallic compound as positive electrode active materials at present, and using carbon materials such as graphite as negative electrode active material, electrolyte is the esters containing lithium salts.But the negative electrode active materials such as graphite occupy substantial portion of volume and weight in the battery, constrain the battery capacity and energy density of lithium ion battery.Lithium ion battery haves the shortcomings that lithium resource reserves are limited, at high cost simultaneously.
Summary of the invention
In order to overcome above-mentioned technical problem, the present invention provides a kind of Magnesium ion battery and preparation method thereof.
In a first aspect, the present invention provides a kind of Magnesium ion battery, including battery cathode, electrolyte, diaphragm and anode；
Wherein, the anode includes plus plate current-collecting body and anode active material layer, and the anode active material layer includes positive electrode active materials, and the anode active material layer includes the positive electrode active materials of freely reversible deintercalation magnesium ion；
The electrolyte includes electrolyte and solvent, and the electrolyte is magnesium salts；
The battery cathode includes one of metal, metal alloy or metal composite conductive material or several
Kind.
Preferably, the metal, metal alloy or metal composite conductive material include the compound or in which the alloy of any one of one of magnesium metal, nickel, tin, zinc, lithium, aluminium, copper, neodymium, lead, antimony, strontium, yttrium, lanthanum, germanium, cobalt, cerium, calcium, beryllium, gold, silver, barium or in which any one metal.
Preferably, the positive electrode active materials include the one or more of the metal oxide of magnesium, metal sulfide or polyanionic compound.
Preferably, the magnesium salts includes one or more of organic type magnesium salts or inorganic type magnesium salts.
Preferably, the concentration range of the magnesium salts is 0.1-10mol/L.
Preferably, the solvent includes one or more of esters, sulfone class, ethers, nitrile organic solvent or imidazoles, piperidines, pyroles, quaternary amines, amides ionic liquid.
Second aspect, the present invention also provides a kind of preparation methods of Magnesium ion battery, this method comprises:
Battery cathode is prepared, the metal of required size, metal alloy or metal composite conductive material is spare as battery cathode after surface treatment.
Electrolyte is prepared, a certain amount of magnesium salts electrolyte is added in coordinative solvent, dissolution is sufficiently stirred.
Diaphragm is prepared, using the porous polymer film of required size or inorganic porous film or organic/inorganic composite diaphragm as battery diaphragm.
Anode is prepared, positive electrode active materials, conductive agent and binder living is weighed by a certain percentage, is fully ground into uniform sizing material in addition appropriate solvent and anode active material layer is made；Using metal, metal alloy or metal composite conductive material as plus plate current-collecting body；Then the anode active material layer is evenly applied to plus plate current-collecting body surface, the anode of size needed for obtaining after the anode active material layer is completely dried.
It is assembled using the battery cathode, electrolyte, diaphragm and anode.
Compared with prior art, the beneficial effects of the present invention are: the present invention provides a kind of Magnesium ion battery, replace lithium with magnesium, solve the problems, such as that lithium resource reserves are limited；While Magnesium ion battery provided by the invention
Battery cathode plays electric action and simultaneously as the material with cationoid reaction in electrolyte, the cathode of middle battery has generally included the collector of electric action and the active material for reacting compared with the prior art, save the volume and weight of a component, it can reduce the weight and volume of battery, improve battery energy density；And the reactive agent of electrochemical reaction that Magnesium ion battery provided by the invention is occurred is magnesium ion, there are two charges for magnesium ion band, improve the capacity of battery.
Fig. 1 is the structural schematic diagram of Magnesium ion battery provided in an embodiment of the present invention.
Invention is further described in detail with reference to the accompanying drawings and detailed description.The following is a preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the principles of the embodiments of the present invention; several improvements and modifications can also be made, these modifications and embellishments are also considered to be within the scope of the present invention.
The present invention provides a kind of Magnesium ion batteries, structure is as shown in Figure 1, including battery cathode 1, electrolyte 2, diaphragm 3 and anode 4, wherein, the anode includes plus plate current-collecting body 42 and anode active material layer 41, and the anode active material layer includes the positive electrode active materials of freely reversible deintercalation magnesium ion；The electrolyte includes electrolyte and solvent, and the electrolyte is magnesium salts；The battery cathode includes one or more of metal, metal alloy or metal composite conductive material.
The embodiment of the present invention, during the charging process, magnesium ion deposit to battery cathode surface from positive electrode abjection, directly react to form magnesium-metal alloy with the metal or metal alloy of battery cathode or metal composite；In discharge process, it is embedded in positive electrode active materials after magnesium-metal alloy de-magging of cathode by electrolyte, to realize reversible charge and discharge.
Battery cathode in the Magnesium ion battery of the embodiment of the present invention plays electric action and simultaneously as the material reacted with magnesium ion, the cathode of middle battery has generally included the collector of electric action and the active material for reacting compared with the prior art, save the volume and weight of a component, the weight and volume of battery is reduced, battery energy density is improved；And the reactive agent of electrochemical reaction that Magnesium ion battery provided by the invention is occurred is magnesium ion, there are two charges for magnesium ion band, and the capacity of battery can be improved；Magnesium ion battery provided by the invention replaces lithium with magnesium simultaneously, solves the problems, such as that lithium resource reserves are limited.
In a preferred embodiment, the positive electrode active materials include but is not limited to the one or more of the metal oxide of magnesium, metal sulfide or polyanionic compound.
In a preferred embodiment, the positive electrode active materials include but is not limited to the metal oxide of magnesium, such as Mgx1MoO3, magnesium ferrite, mangaic acid magnesium, vanadic acid magnesium, vanadium magnesium ferrite, magnesium stannate, spinel-type MgCo0.4Mn1.6O4、MgM2O4；The metal sulfide of magnesium, such as Mgx2Mo3S4, Mgx3NS2；The polyanionic compound of magnesium, such as the silicate series MgASiO of orthohormbic structure4, sulfate series MgASO4, series of phosphate MgAPO4One or more of.The wherein any number of x1, x2, x3 between 0-1, M Mn, Ni, Co, Fe, Zn, Ti or Al, N Ti, Zr, Hf, Nb, Ta, Mo, W or V, A Fe, Mn, Ni, Al, V, Ti, Zn or Co.
In a preferred embodiment, the metal, metal alloy or metal composite conductive material include but is not limited to the compound or in which the alloy of any one of one of magnesium metal, nickel, tin, zinc, lithium, aluminium, copper, neodymium, lead, antimony, strontium, yttrium, lanthanum, germanium, cobalt, cerium, calcium, beryllium, gold, silver, barium or in which any one metal, as long as deposition dissolution magnesium or form alloy with magnesium that the metal can be reversible, the present invention does not limit the type of metal.
Cathode of the invention, also using other metal or alloy materials or compound that alloying reaction can occur with magnesium, increases the alternative of negative electrode material other than magnesium metal or alloy material.
In a preferred embodiment, the plus plate current-collecting body include but is not limited to aluminium, lithium, magnesium,
The compound or in which the alloy of any one of one of vanadium, copper, iron, tin, zinc, nickel, titanium, manganese or in which any one metal.
In the embodiment of the present invention, the anode active material layer further includes conductive agent and binder.
In a preferred embodiment, the anode active material layer, by weight percentage, including 60~90wt% positive electrode active materials.
In a preferred embodiment, the anode active material layer, by weight percentage, including 0.1~30wt% conductive agent.
In a preferred embodiment, the anode active material layer, by weight percentage, including 0.1~10wt% binder.
It is understood that the binder and conductive agent in the anode active material layer are it is not also specifically limited, this field is existing common common.
In a preferred embodiment, the conductive agent is one or more of black conductive acetylene, conductive carbon ball, electrically conductive graphite, carbon nanotube, graphene.
In a preferred embodiment, the binder is one or more of Kynoar, polytetrafluoroethylene (PTFE), polyvinyl alcohol, carboxymethyl cellulose, butadiene-styrene rubber, polyolefins.
In the embodiment of the present invention, electrolyte is magnesium salts, including one or more of organic type magnesium salts or inorganic type magnesium salts.
In one embodiment of the present invention, the concentration range of the magnesium salts is 0.1-10mol/L.
In one embodiment of the present invention, the organic type magnesium salts includes but is not limited to RMgX, methylphenylamine magnesium bromide, pyrrole radicals magnesium bromide, ethylenediamine tetraacetic acid disodium magnesium salt (EDTA-Mg), N, N- bis- (trimethyl silicon substrate) amino magnesium chloride, Mg (SnPh3)2、Mg(BR2R'2)2、Mg(AZ3-nRn'R'n”)2One or more of type complex, wherein R is alkyl, and X is halogen, A Al, B, As, P, Sb, Ta or Fe, and Z is Cl or Br, and R' is aryl, and n'+n "=n.
In one embodiment of the present invention, the inorganic type magnesium salts includes but is not limited to Mg (ClO4)2、Mg(BF4)2、Mg(PF6)2、MgCl2、MgBr2、MgF2、MgI2、Mg(NO3)2、MgSO4、Mg(SCN)2、MgCrO4、Mg(CF3SO3)2One or more of.
It is understood that the solvent is not particularly limited, as long as making ion can be with free migration.
In a preferred embodiment, the solvent includes but is not limited to one or more of esters, sulfone class, ethers, nitrile organic solvent or imidazoles, piperidines, pyroles, quaternary amines, amides ionic liquid.
In a preferred embodiment, the solvent is selected from propene carbonate, ethylene carbonate, butylene, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, dibutyl carbonate, carbonic acid first butyl ester, carbonic acid first isopropyl ester, methyl esters, methyl formate, methyl acetate, N, N- dimethyl acetamide, fluorinated ethylene carbonate, methyl propionate, ethyl propionate, ethyl acetate, gamma-butyrolacton, tetrahydrofuran, 2- methyltetrahydrofuran, 1, 3- dioxolanes, 4- methyl-1, 3- dioxolanes, dimethoxymethane, 1, 2- dimethoxy, 1, 2- diformazan Ethylene Oxide, triethylene glycol dimethyl ether, dimethyl sulfone, acetonitrile, dimethyl ether, ethylene sulfite, sulfurous acid propylene rouge, two formicester of sulfurous acid, sulfurous acid diethyl rouge, crown ether, 1- Ethyl-3-methylimidazole-hexafluorophosphate, 1- ethyl-3-methylimidazole-tetrafluoroborate, 1- ethyl-3-methylimidazole-bis trifluoromethyl sulfimide salt, 1- propyl -3- methylimidazole-hexafluorophosphate, 1- propyl -3- methylimidazole-tetrafluoroborate, 1- propyl -3- methylimidazole-bis trifluoromethyl sulfimide salt, 1- butyl -1- methylimidazole-hexafluorophosphate, 1- butyl -1- methylimidazole-tetrafluoroborate, 1- butyl -1- methylimidazole-bis trifluoromethyl sulfimide salt, N- butyl-N- methylpyrrolidin- bis trifluoromethyl sulfimide salt, 1- butyl -1- methylpyrrolidin- bis trifluoromethyl sulfimide salt, N- Methyl-N-propyl pyrrolidines-bis trifluoromethyl sulfimide salt, N- first, propylpiperdine- Bis trifluoromethyl sulfimide salt, N- first, one or more of butyl piperidine-bis trifluoromethyl sulfimide salt.
In a preferred embodiment, the solvent is ethers, compares other kinds of solvent, ether
The stronger ethers of class especially polarity will not form oxide layer on the metal or metal alloy of battery cathode or metal composite surface, be conducive to when charge and discharge magnesium ion in the deposition or abjection of battery cathode.
Specifically, the ether solvent include but is not limited to include tetrahydrofuran (THF), 2- methyltetrahydrofuran (2Me-THF), 1, one or more of 3- dioxolanes (DN), Isosorbide-5-Nitrae-dioxane, diethyl ether (DEE), glycol dimethyl ether (DME) and tetraethyleneglycol dimethyl ether.
In a preferred embodiment, additive, such as LiCl can be added in the electrolyte, and the effect of additive is the comprehensive performances such as high temperature performance, security performance, the cycle performance for improving the ionic conductivity of electrolyte or improving battery.
It is understood that the diaphragm is it is not also specifically limited, existing common common using this field.
In an embodiment of the present invention, the diaphragm includes but is not limited to the porous polymer film or inorganic porous film to insulate.
In a preferred embodiment, the diaphragm includes but is not limited to porous polypropylene film, porous polyethylene film, porous compound polymer film, non-woven fabrics, all-glass paper or porous ceramics diaphragm.
In a preferred embodiment, the diaphragm is all-glass paper or non-woven fabrics.
It is understood that the form of Magnesium ion battery provided by the present invention is not particularly limited, it is commonly used in the art, such as the forms such as button cell, flat plate cell, cylindrical battery.
Second aspect, the embodiment of the invention also provides the methods for preparing above-mentioned Magnesium ion battery, comprising:
Step 101, preparation battery cathode, the metal of required size, metal alloy or metal composite conductive material is spare as battery cathode after surface treatment.
Specifically, metal, metal alloy or metal composite conductive material are selected from one of magnesium metal, nickel, tin, zinc, lithium, aluminium, copper, neodymium, lead, antimony, strontium, yttrium, lanthanum, germanium, cobalt, cerium, calcium, beryllium, gold, silver, barium or in which the compound or in which the alloy of any one of any one metal.
Step 102 prepares electrolyte, and a certain amount of magnesium salts electrolyte is added in coordinative solvent, dissolution is sufficiently stirred.
The magnesium salts electrolyte specifically includes one or more of organic type magnesium salts or inorganic type magnesium salts.
Specifically, the organic type magnesium salts includes RMgX, methylphenylamine magnesium bromide, pyrrole radicals magnesium bromide, ethylenediamine tetraacetic acid disodium magnesium salt (EDTA-Mg), N, N- bis- (trimethyl silicon substrate) amino magnesium chloride, Mg (SnPh3)2、Mg(BR2R'2)2、Mg(AZ3-nRn'R'n”)2One or more of type complex.Wherein, R is alkyl, and X is halogen, A Al, B, As, P, Sb, Ta or Fe, and Z is Cl or Br, and R' is aryl, and n'+n "=n.
Specifically, the inorganic type magnesium salts includes Mg (ClO4)2、Mg(BF4)2、Mg(PF6)2、MgCl2、MgBr2、MgF2、MgI2、Mg(NO3)2、MgSO4、Mg(SCN)2、MgCrO4、Mg(CF3SO3)2One or more of.
Specifically, the magnesium salts is obtained by directly purchase or by the way that two kinds of solution allocations reacts acquisition together.
The solvent includes but is not limited to esters, sulfone class, ethers, nitrile organic solvent or imidazoles, piperidines, pyroles, quaternary amines, one or more of amides ionic liquid, selected from propene carbonate, ethylene carbonate, butylene, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, dibutyl carbonate, carbonic acid first butyl ester, carbonic acid first isopropyl ester, methyl esters, methyl formate, methyl acetate, N, N- dimethyl acetamide, fluorinated ethylene carbonate, methyl propionate, ethyl propionate, ethyl acetate, gamma-butyrolacton, tetrahydrofuran, 2- methyltetrahydrofuran, 1, 3- dioxolanes, 4- methyl-1, 3- dioxolanes, dimethoxymethane, 1, 2- dimethoxy, 1, 2- diformazan Ethylene Oxide, triethylene glycol dimethyl ether, dimethyl sulfone , acetonitrile, dimethyl ether, ethylene sulfite, sulfurous acid propylene rouge, two formicester of sulfurous acid, sulfurous acid diethyl rouge, crown ether, 1- ethyl-3-methylimidazole-hexafluorophosphate, 1- ethyl-3-methylimidazole-tetrafluoroborate, 1- ethyl-3-methylimidazole-bis trifluoromethyl sulfimide salt, 1- propyl -3- methylimidazole-hexafluorophosphate,
1- propyl -3- methylimidazole-tetrafluoroborate, 1- propyl -3- methylimidazole-bis trifluoromethyl sulfimide salt, 1- butyl -1- methylimidazole-hexafluorophosphate, 1- butyl -1- methylimidazole-tetrafluoroborate, 1- butyl -1- methylimidazole-bis trifluoromethyl sulfimide salt, N- butyl-N- methylpyrrolidin- bis trifluoromethyl sulfimide salt, 1- butyl -1- methylpyrrolidin- bis trifluoromethyl sulfimide salt, N- Methyl-N-propyl pyrrolidines-bis trifluoromethyl sulfimide salt, N- first, propylpiperdine-bis trifluoromethyl sulfimide salt, N- first, one or more of butyl piperidine-bis trifluoromethyl sulfimide salt.
The magnesium salts electrolyte is added in the solvent, dissolution is sufficiently stirred, the concentration range of magnesium salts described in the electrolyte of configuration is 0.1-10mol/L.
Step 103 prepares diaphragm, using the porous polymer film of required size or inorganic porous film or organic/inorganic composite diaphragm as battery diaphragm.
Specifically, the porous polymer film or inorganic porous film include but is not limited to porous polypropylene film, porous polyethylene film, porous compound polymer film, non-woven fabrics, all-glass paper or porous ceramics diaphragm.
Step 104 prepares anode, weighs positive electrode active materials, conductive agent and binder living by a certain percentage, is fully ground into uniform sizing material in addition appropriate solvent and anode active material layer is made；Using metal, metal alloy or metal composite conductive material as plus plate current-collecting body；Then the anode active material layer is evenly applied to plus plate current-collecting body surface, the anode of size needed for obtaining after the anode active material layer is completely dried.
Plus plate current-collecting body plus plate current-collecting body is metal, metal alloy or metal composite conductive material, can be selected from one of aluminium, magnesium, vanadium, lithium, copper, iron, tin, zinc, nickel, titanium, manganese or in which the compound or in which the alloy of any one of any one metal.
The deal of positive electrode active materials is 60-90wt% in anode active material layer, and the content of conductive agent is 0.1-30wt%, and the content of binder is 0.1-10wt%.
The positive electrode active materials include but is not limited to one or more of metal oxide, metal sulfide, polyanionic compound of magnesium.
The conductive agent includes but is not limited to one or more of black conductive acetylene, conductive carbon ball, electrically conductive graphite, carbon nanotube, graphene.
The binder includes but is not limited to one or more of Kynoar, polytetrafluoroethylene (PTFE), polyvinyl alcohol, carboxymethyl cellulose, butadiene-styrene rubber, polyolefins
Step 105 is assembled using the battery cathode, electrolyte, diaphragm and anode.
Specifically include: under inert gas or anhydrous and oxygen-free environment, by the cathode prepared, diaphragm, anode, successively Close stack, dropwise addition electrolyte make diaphragm complete wetting, are then encapsulated into battery case, complete battery assembly.
It should be noted that although above-mentioned steps 101-104 is to describe the operation of preparation method of the present invention with particular order, this does not require that or implies must execute these operations in this particular order.The preparation of step 101-104 simultaneously or arbitrarily can be executed successively.
The Magnesium ion battery preparation method and aforementioned Magnesium ion battery are that based on the same inventive concept, have the institute of aforementioned Magnesium ion battery effective using the Magnesium ion battery that the Magnesium ion battery preparation method obtains, details are not described herein.
Above-mentioned Magnesium ion battery preparation method is further illustrated below by specific embodiment, it should be understood, however, that, these embodiments, which are only used for being described in more detail, to be used, and but should not be understood as present invention is limited in any form.
Embodiment 1
Preparation battery cathode: taking the aluminium foil with a thickness of 0.02mm, cut into the disk of diameter 12mm, spare as negative current collector after surface treatment.
It prepares diaphragm: all-glass paper is cut into the disk of diameter 16mm, it is spare as diaphragm after drying.
It prepares electrolyte: measuring 2.5ml MgBu2Solution and 2.5ml AlCl2The mixing of Et solution, then will be molten
Agent is distilled off, by reaction product Mg (AlCl2BuEt)2It is added into appropriate high-purity tetrahydrofuran solution spare as electrolyte.
It prepares anode: 0.4g magnesium ferrite, 0.1g carbon black, 0.1g Kynoar being added in 2ml N-methyl pyrrolidone solution, acquisition uniform sizing material is fully ground；Then slurry is evenly applied to aluminium foil surface and be dried in vacuo.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as anode after compacting.
Battery assembly: in the glove box of inert gas shielding; by the above-mentioned negative current collector prepared, diaphragm, anode successively Close stack; electrolyte, which is added dropwise, makes diaphragm complete wetting, and above-mentioned stacking portion is then encapsulated into button cell shell, completes battery assembly.
Embodiment 2
Preparation battery cathode: taking the nickel foil with a thickness of 0.02mm, cut into the disk of diameter 12mm, spare as negative current collector after surface treatment.
It prepares diaphragm: all-glass paper is cut into the disk of diameter 16mm, it is spare as diaphragm after drying.
It prepares electrolyte: measuring 4.5ml N, (trimethyl silicon substrate) the amino magnesium chloride solution of N- bis- and 1.5ml AlCl3Solution mixing, then solvent is distilled off, by reaction product [Mg2(μ-Cl)3·6THF][HMDSAlCl3] be added into appropriate high-purity tetrahydrofuran solution it is spare as electrolyte.
It prepares anode: 0.4g manganous silicate magnesium material, 0.1g carbon black, 0.1g Kynoar being added in 2ml N-methyl pyrrolidone solution, acquisition uniform sizing material is fully ground；Then slurry is evenly applied to aluminium foil surface and be dried in vacuo.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as anode after compacting.
Battery assembly: in the glove box of inert gas shielding, by the above-mentioned negative current collector prepared, diaphragm, anode successively Close stack, electrolyte, which is added dropwise, makes diaphragm complete wetting, then by above-mentioned stack portion
Enfeoffment is packed into button cell shell, completes battery assembly.
Embodiment 3
Preparation battery cathode: taking the nickel foil with a thickness of 0.02mm, cut into the disk of diameter 12mm, spare as negative current collector after surface treatment.
It prepares diaphragm: porous polyethylene film is cut into the disk of diameter 16mm, it is spare as diaphragm after drying.
It prepares electrolyte: weighing 2.15g ethylenediamine tetraacetic acid disodium magnesium salt (EDTA-Mg) and be added in 5ml formamide (FA), be stirred well to after ethylenediamine tetraacetic acid disodium magnesium salt is completely dissolved spare as electrolyte.
Prepare anode: by 0.4gMgxMo3S4, 0.1g carbon black, 0.1g Kynoar be added in 2ml N-methyl pyrrolidone solution, be fully ground acquisition uniform sizing material；Then slurry is evenly applied to aluminium foil surface and be dried in vacuo.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as anode after compacting.
Battery assembly: in the glove box of inert gas shielding; by the above-mentioned negative current collector prepared, diaphragm, anode successively Close stack; electrolyte, which is added dropwise, makes diaphragm complete wetting, and above-mentioned stacking portion is then encapsulated into button cell shell, completes battery assembly.
Embodiment 4
Preparation battery cathode: taking the tinfoil paper with a thickness of 0.02mm, cut into the disk of diameter 12mm, spare as negative current collector after surface treatment.
It prepares diaphragm: non-woven fabrics is cut into the disk of diameter 16mm, it is spare as diaphragm after drying.
It prepares electrolyte: weighing 0.5M pyrrole radicals magnesium bromide and be added in tetrahydrofuran (THF), be stirred well to after pyrrole radicals magnesium bromide is completely dissolved spare as electrolyte.
Prepare anode: by 0.4gMgCo0.4Mn1.6O4, 0.1g carbon black, 0.1g Kynoar be added in 2ml N-methyl pyrrolidone solution, be fully ground acquisition uniform sizing material；Then slurry is evenly applied to aluminium foil surface and be dried in vacuo.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as anode after compacting.
Battery assembly: in the glove box of inert gas shielding; by the above-mentioned negative current collector prepared, diaphragm, anode successively Close stack; electrolyte, which is added dropwise, makes diaphragm complete wetting, and above-mentioned stacking portion is then encapsulated into button cell shell, completes battery assembly.
Embodiment 5
Preparation battery cathode: taking the zinc foil with a thickness of 0.02mm, cut into the disk of diameter 12mm, spare as negative current collector after surface treatment.
It prepares diaphragm: porous ceramics diaphragm is cut into the disk of diameter 16mm, it is spare as diaphragm after drying.
It prepares electrolyte: weighing 1.11g magnesium perchlorate and be added in 2.5ml acetonitrile and 2.5ml ethylene carbonate, be stirred well to after magnesium perchlorate is completely dissolved spare as electrolyte.
It prepares anode: 0.4g titanium phosphate magnesium, 0.1g carbon black, 0.1g Kynoar being added in 2ml N-methyl pyrrolidone solution, acquisition uniform sizing material is fully ground；Then slurry is evenly applied to aluminium foil surface and be dried in vacuo.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as anode after compacting.
Battery assembly: in the glove box of inert gas shielding; by the above-mentioned negative current collector prepared, diaphragm, anode successively Close stack; electrolyte, which is added dropwise, makes diaphragm complete wetting, and above-mentioned stacking portion is then encapsulated into button cell shell, completes battery assembly.
Embodiment 6
Preparation battery cathode: taking the aluminium foil with a thickness of 0.02mm, cut into the disk of diameter 12mm, spare as negative current collector after surface treatment.
It prepares diaphragm: porous composite polymer membranes is cut into the disk of diameter 16mm, it is spare as diaphragm after drying.
It prepares electrolyte: weighing 0.475g magnesium chloride and be added in 2.5ml tetrahydrofuran (THF) and 2.5ml ethylene carbonate, be stirred well to after magnesium chloride is completely dissolved spare as electrolyte.
It prepares anode: 0.4g vanadium magnesium ferrite, 0.1g carbon black, 0.1g Kynoar being added in 2ml N-methyl pyrrolidone solution, acquisition uniform sizing material is fully ground；Then slurry is evenly applied to aluminium foil surface and be dried in vacuo.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as anode after compacting.
Battery assembly: in the glove box of inert gas shielding; by the above-mentioned negative current collector prepared, diaphragm, anode successively Close stack; electrolyte, which is added dropwise, makes diaphragm complete wetting, and above-mentioned stacking portion is then encapsulated into button cell shell, completes battery assembly.
Embodiment 7
Preparation battery cathode: taking the aluminium foil with a thickness of 0.02mm, is used as negative current collector spare after cutting into the disk surfaces processing of diameter 12mm.
It prepares diaphragm: all-glass paper is cut into the disk of diameter 16mm, it is spare as diaphragm after drying.
It prepares electrolyte: weighing 2.22g magnesium perchlorate and be added to 5ml n,N-Dimethylformamide (DMF), be stirred well to after magnesium perchlorate is completely dissolved spare as electrolyte.
It prepares anode: 0.4g vanadic acid magnesium, 0.1g carbon black, 0.1g Kynoar being added in 2ml N-methyl pyrrolidone solution, acquisition uniform sizing material is fully ground；Then slurry is evenly applied to aluminium foil table
Face is simultaneously dried in vacuo.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as anode after compacting.
Battery assembly: in the glove box of inert gas shielding; by the above-mentioned negative current collector prepared, diaphragm, anode successively Close stack; electrolyte, which is added dropwise, makes diaphragm complete wetting, and above-mentioned stacking portion is then encapsulated into button cell shell, completes battery assembly.
Embodiment 8
Preparation battery cathode: taking the aluminium foil with a thickness of 0.02mm, cut into the disk of diameter 12mm, spare as negative current collector after surface treatment.
It prepares diaphragm: all-glass paper is cut into the disk of diameter 16mm, it is spare as diaphragm after drying.
It prepares electrolyte: weighing 3.22gMg (CF3SO3)2It is added to 10mlN- Methyl-N-propyl pyrrolidines-bis trifluoromethyl sulfimide salt, is stirred well to Mg (CF3SO3)2It is spare as electrolyte after being completely dissolved.
It prepares anode: 0.4g cobalt phosphate magnesium, 0.1g carbon black, 0.1g Kynoar being added in 2ml N-methyl pyrrolidone solution, acquisition uniform sizing material is fully ground；Then slurry is evenly applied to aluminium foil surface and be dried in vacuo.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as anode after compacting.
Battery assembly: in the glove box of inert gas shielding; by the above-mentioned negative current collector prepared, diaphragm, anode successively Close stack; electrolyte, which is added dropwise, makes diaphragm complete wetting, and above-mentioned stacking portion is then encapsulated into button cell shell, completes battery assembly.
Magnesium ion battery form of the present invention is not limited to button cell, and the forms such as flat plate cell, cylindrical battery can also be designed to according to core component.
Particular embodiments described above has been further described the purpose of the present invention, technical scheme and beneficial effects, it should be understood that the above is only a specific embodiment of the present invention, not
For limiting the scope of protection of the present invention, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done be should all be included in the protection scope of the present invention.
Claims (7)
- A kind of Magnesium ion battery, including battery cathode, electrolyte, diaphragm and anode, which is characterized in thatWherein, the anode includes plus plate current-collecting body and anode active material layer, and the anode active material layer includes positive electrode active materials, and the anode active material layer includes the positive electrode active materials of freely reversible deintercalation magnesium ion；The electrolyte includes electrolyte and solvent, and the electrolyte is magnesium salts；The battery cathode includes one or more of metal, metal alloy or metal composite conductive material.
- Magnesium ion battery as described in claim 1, it is characterized in that, the metal, metal alloy or metal composite conductive material include the compound or in which the alloy of any one of one of magnesium metal, nickel, tin, zinc, lithium, aluminium, copper, neodymium, lead, antimony, strontium, yttrium, lanthanum, germanium, cobalt, cerium, calcium, beryllium, gold, silver, barium or in which any one metal.
- Magnesium ion battery as described in claim 1, which is characterized in that the positive electrode active materials include the one or more of the metal oxide of magnesium, metal sulfide or polyanionic compound.
- Secondary cell as described in claim 1, which is characterized in that the magnesium salts includes one or more of organic type magnesium salts or inorganic type magnesium salts.
- Magnesium ion battery as described in claim 1, which is characterized in that the concentration range of the magnesium salts is 0.1-10mol/L.
- Magnesium ion battery as described in claim 1, which is characterized in that the solvent includes one or more of esters, sulfone class, ethers, nitrile organic solvent or imidazoles, piperidines, pyroles, quaternary amines, amides ionic liquid.
- A kind of preparation method preparing the Magnesium ion battery as described in one of claim 1-6, feature exist In, comprising:Battery cathode is prepared, the metal of required size, metal alloy or metal composite conductive material is spare as battery cathode after surface treatment；Electrolyte is prepared, a certain amount of magnesium salts electrolyte is weighed and is added in coordinative solvent, dissolution is sufficiently stirred；Diaphragm is prepared, using the porous polymer film of required size or inorganic porous film or organic/inorganic composite diaphragm as battery diaphragm；Anode is prepared, positive electrode active materials, conductive agent and binder living is weighed by a certain percentage, is fully ground into uniform sizing material in addition appropriate solvent and anode active material layer is made；Using metal, metal alloy or metal composite conductive material as plus plate current-collecting body；Then the anode active material layer is evenly applied to plus plate current-collecting body surface, the anode of size needed for obtaining after the anode active material layer is completely dried；It is assembled using the battery cathode, electrolyte, diaphragm and anode.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2016/084113 WO2017206063A1 (en) | 2016-05-31 | 2016-05-31 | Magnesium ion battery and preparation method therefor |
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| CN109196701A true CN109196701A (en) | 2019-01-11 |
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| CN201680085081.7A Pending CN109196701A (en) | 2016-05-31 | 2016-05-31 | A kind of Magnesium ion battery and preparation method thereof |
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| WO (1) | WO2017206063A1 (en) |
Cited By (5)
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| CN110197929A (en) * | 2019-05-22 | 2019-09-03 | 佛山科学技术学院 | The preprocess method and Magnesium ion battery of Magnesium ion battery negative electrode material |
| CN112573572A (en) * | 2020-12-28 | 2021-03-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of magnesium vanadyl acid nano material, product and application thereof |
| CN113488633A (en) * | 2021-07-27 | 2021-10-08 | 广西师范大学 | Titanium magnesium phosphate coated high-nickel ternary or lithium-rich manganese-based positive electrode material and preparation method thereof |
| CN115036469A (en) * | 2022-06-02 | 2022-09-09 | 重庆大学 | Preparation method of metal magnesium negative electrode artificial SEI capable of reversibly circulating in traditional electrolyte and product |
| WO2023011115A1 (en) * | 2021-08-04 | 2023-02-09 | 中国科学院青岛生物能源与过程研究所 | Magnesium negative electrode polymer protective layer, preparation method therefor and application thereof |
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| DE102022101871A1 (en) * | 2022-01-27 | 2023-07-27 | Honda Motor Co., Ltd. | Coating for magnesium electrodes |
| CN118908278B (en) * | 2024-08-06 | 2025-12-12 | 烟台大学 | Preparation methods and applications of amorphous MoS5+x magnesium ion battery cathode materials |
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| CN113488633A (en) * | 2021-07-27 | 2021-10-08 | 广西师范大学 | Titanium magnesium phosphate coated high-nickel ternary or lithium-rich manganese-based positive electrode material and preparation method thereof |
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| WO2017206063A1 (en) | 2017-12-07 |
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