CN115020670A - MOFs modified silicon-based negative electrode material and preparation method thereof - Google Patents
MOFs modified silicon-based negative electrode material and preparation method thereof Download PDFInfo
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- CN115020670A CN115020670A CN202210757629.5A CN202210757629A CN115020670A CN 115020670 A CN115020670 A CN 115020670A CN 202210757629 A CN202210757629 A CN 202210757629A CN 115020670 A CN115020670 A CN 115020670A
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- silicon
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 76
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 77
- 239000010703 silicon Substances 0.000 claims abstract description 77
- 150000003376 silicon Chemical class 0.000 claims abstract description 56
- 239000002243 precursor Substances 0.000 claims abstract description 52
- 238000010438 heat treatment Methods 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 230000004048 modification Effects 0.000 claims abstract description 24
- 238000012986 modification Methods 0.000 claims abstract description 24
- 239000013110 organic ligand Substances 0.000 claims abstract description 21
- 239000012266 salt solution Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 150000003751 zinc Chemical class 0.000 claims abstract description 12
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 79
- 238000000034 method Methods 0.000 claims description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 34
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 11
- 239000010405 anode material Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- NIJMZBWVSRWZFZ-UHFFFAOYSA-N 4-[2-[3,5-bis[2-(4-carboxyphenyl)ethynyl]phenyl]ethynyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C#CC1=CC(C#CC=2C=CC(=CC=2)C(O)=O)=CC(C#CC=2C=CC(=CC=2)C(O)=O)=C1 NIJMZBWVSRWZFZ-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- HJCNSOVRAZFJLK-UHFFFAOYSA-N C1=CC(C(=O)O)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 HJCNSOVRAZFJLK-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 239000005049 silicon tetrachloride Substances 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- -1 4-carboxyphenyl Chemical group 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005052 trichlorosilane Substances 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 2
- MTTUYJXPONEHGK-UHFFFAOYSA-N 4-[2-(4-carboxyphenyl)-1,2-diphenylethenyl]benzoic acid Chemical group C1=CC(C(=O)O)=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC(=CC=1)C(O)=O)C1=CC=CC=C1 MTTUYJXPONEHGK-UHFFFAOYSA-N 0.000 claims description 2
- PAPDRIKTCIYHFI-UHFFFAOYSA-N 4-[3,5-bis(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC(OC=2C=CC(N)=CC=2)=CC(OC=2C=CC(N)=CC=2)=C1 PAPDRIKTCIYHFI-UHFFFAOYSA-N 0.000 claims description 2
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- VWAIZPYLEYEEFK-UHFFFAOYSA-N adamantane-1,3,5,7-tetracarboxylic acid Chemical compound C1C(C2)(C(O)=O)CC3(C(O)=O)CC1(C(=O)O)CC2(C(O)=O)C3 VWAIZPYLEYEEFK-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 229960001841 potassium permanganate Drugs 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000956 alloy Substances 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- DTWCOCYXNRTSIA-UHFFFAOYSA-N C(C)O.[N+](=O)([O-])[O-].[Zn+2].[N+](=O)([O-])[O-] Chemical compound C(C)O.[N+](=O)([O-])[O-].[Zn+2].[N+](=O)([O-])[O-] DTWCOCYXNRTSIA-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000004729 solvothermal method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- GANMEEJISNNTGT-UHFFFAOYSA-N ethanol;2-methyl-1h-imidazole Chemical compound CCO.CC1=NC=CN1 GANMEEJISNNTGT-UHFFFAOYSA-N 0.000 description 7
- 238000005275 alloying Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- RROAJOQUFRGVRG-UHFFFAOYSA-L dichlorozinc;ethanol Chemical compound [Cl-].[Cl-].[Zn+2].CCO RROAJOQUFRGVRG-UHFFFAOYSA-L 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- ZMWWBERCRBOAGU-UHFFFAOYSA-N silver;propan-2-one;nitrate Chemical compound [Ag+].CC(C)=O.[O-][N+]([O-])=O ZMWWBERCRBOAGU-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QXOGVNFCFLZICX-UHFFFAOYSA-M chlorosilver pyridine Chemical compound [Ag]Cl.N1=CC=CC=C1 QXOGVNFCFLZICX-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000013082 iron-based metal-organic framework Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000013239 manganese-based metal-organic framework Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- UBNXKGZRBIGKGD-UHFFFAOYSA-N silver toluene nitrate Chemical compound C1(=CC=CC=C1)C.[N+](=O)([O-])[O-].[Ag+] UBNXKGZRBIGKGD-UHFFFAOYSA-N 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000013094 zinc-based metal-organic framework Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a MOFs modified silicon-based negative electrode material and a preparation method thereof, wherein the preparation method comprises the following steps: preparing a precursor liquid containing a silicon source and a metal salt; adding a first organic ligand into the precursor liquid for reaction to carry out MOFs modification, drying the coated plate, and carrying out heat treatment to obtain a MOFs modified silicon-based precursor material; and (3) placing the MOFs modified silicon-based precursor material into a zinc salt solution, adding a second organic ligand for hydrophobic modification, and drying to obtain the MOFs modified silicon-based negative electrode material. According to the invention, the conductive performance of the silicon-based negative electrode material can be obviously improved by introducing the alloy element and the carbon skeleton, the conductive performance of the silicon-based negative electrode material is enhanced, and the electrochemical performance of the silicon-based negative electrode material is favorably improved after the metal ions are reasonably doped; the dispersibility of the silicon-based negative electrode material is improved through hydrophobic modification, so that the volume expansion hazard of the silicon-carbon negative electrode material is reduced.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a MOFs modified silicon-based negative electrode material and a preparation method thereof.
Background
Lithium ion batteries have the advantages of high energy storage density, high open circuit voltage, low self-discharge rate, and the like, and are widely used in recent years. At present, the commercialized lithium battery adopts graphite carbon as a negative electrode material, but the theoretical capacity of graphite is only 372mAh/g, and the rate capability is not good. The theoretical specific capacity of silicon is up to 4200mAh/g, which is one order of magnitude higher than that of graphite cathode materials, and the silicon has moderate lithium intercalation/deintercalation potential, low reactivity with electrolyte, abundant storage in earth crust and low price, thus being an ideal choice for the cathode materials of the new generation of lithium ion batteries.
However, during the alloying reaction process of silicon and lithium, the silicon material can generate violent volume expansion (> 300%), which easily causes the active material to generate sharp pulverization and shedding during the circulation process, and the electric contact between the electrode active material and a current collector is weakened, so that the cycle life of the battery is rapidly reduced. Meanwhile, due to the volume expansion effect of the silicon material, the silicon material cannot generate a firm Solid Electrolyte Interface (SEI) film in the Electrolyte, the electrode structure is damaged, and a new SEI film is continuously formed on the newly exposed silicon surface, so that the charge and discharge efficiency is reduced, and the capacity attenuation is accelerated. Therefore, how to improve the conductivity of the silicon anode material and reduce the expansion problem during the cycle is a big research focus in the field. Chinese patent application publication No. CN109671928A discloses a method for preparing a MOFs-carbonized-coated silicon-based negative electrode material, in which highly dispersed nano-silicon is coated with an ordered and stable structure of a metal-organic framework material, and then carbonized by heat treatment under an inert atmosphere condition to obtain a silicon-based negative electrode material, and the system also contains uniformly dispersed metal nanoparticles, which not only can effectively alleviate the volume change of the nano-silicon and is beneficial to the improvement of the conductivity of the system, but only adopts a primary organic substance for coordination, and the obtained negative electrode material still has the defects of poor cycle life and large volume expansion effect.
Disclosure of Invention
The invention aims to solve the technical problems that the conventional silicon-based negative electrode material is poor in cycle life and large in volume expansion effect, and the quality controllability is poor due to poor dispersibility when the silicon-carbon negative electrode material is actually formed with a carbon material.
The invention solves the technical problems through the following technical means:
a preparation method of a MOFs modified silicon-based negative electrode material comprises the following steps:
s1, preparing a precursor liquid containing a silicon source and a metal salt;
s2, adding a first organic ligand into the precursor liquid in the S1 to react to perform MOFs modification, and carrying out heat treatment after coating and drying to obtain a MOFs modified silicon-based precursor material;
s3, placing the MOFs modified silicon-based precursor material in the S2 in a zinc salt solution, adding a second organic ligand for hydrophobic modification, and drying to obtain the MOFs modified silicon-based negative electrode material.
Has the advantages that: in the technical scheme of the invention, the conductivity of the silicon cathode material taking carbon as a network framework is greatly improved by introducing a reticular MOFs structure, and the alloying can effectively avoid the problem of serious volume expansion generated by conventional alloying and realize the organic matching of the silicon base material and metal. Meanwhile, after the MOFs particles introduced with the metal salt are modified, the conductivity and the electrochemical performance of the silicon-based negative electrode material can be greatly improved, so that the rate capability and the cycle performance of the silicon-based negative electrode material are remarkably improved; and further carrying out secondary modification on the formed granular silicon MOFs carrier by MOFs particles, so that the silicon-based negative electrode material has certain hydrophobicity, the dispersibility of the silicon-based negative electrode material can be obviously improved, and when the silicon-carbon negative electrode material is used for preparing the silicon-carbon negative electrode material, a gap core-shell structure can be effectively formed, namely, the core-shell separation is not contacted with each other, so that the adverse effect caused by the volume expansion of silicon is reduced.
Preferably, in S1, the silicon source includes one or more of trichlorosilane, silicon tetrachloride, ethyl orthosilicate and sodium silicate; the metal salt comprises one or more of silver salt, manganese salt and ferric salt.
Preferably, in S1, the metal salt includes one or more of silver nitrate, silver chloride, silver bromide, manganese chloride, manganese sulfate, manganese acetate, potassium permanganate, ferric chloride hexahydrate, ferric nitrate, and ferric sulfate.
Preferably, in S1, a silicon source is dissolved in a group a solvent to obtain a silicon solution, and a metal salt is dissolved in a group B solvent to obtain a salt solution; mixing a silicon solution with a salt solution to obtain a precursor solution containing a silicon source and a metal salt; the A-type solvent comprises one or more of benzene, chloroform, diethyl ether and petroleum ether; the B-type solvent comprises one or more of benzene, toluene, pentane, hexane, cyclohexane, cyclohexanone, methylcyclohexanone, diethyl ether, epoxypropane, methyl acetate, ethyl acetate, propyl acetate, acetone, methyl butanone, methyl isobutyl ketone, ethylene glycol monomethyl ether, acetonitrile, pyridine and phenol.
Preferably, the molar concentration of the silicon element in the silicon solution is 0.1-1.0 mol/L; the molar concentration of metal ions in the salt solution is 0.1-1.0 mol/L; the molar ratio of silicon element to metal ion in the precursor liquid after the silicon solution and the salt solution are mixed is 1: 0.5-2.
Preferably, in S2, the first organic ligand is one or more of carboxylic acid organic ligand, ammonia organic ligand and pyridine organic ligand; the molar usage of the first organic ligand is 0.125-0.5 times of the total molar weight of the silicon element and the metal ions in the precursor liquid in S1.
Preferably, the first organic ligand is one or a mixture of more of 5, 15-bis (4' -carboxyphenyl) porphyrin, 1, 2-bis (4-carboxyphenyl) -1, 2-stilbene, 5,10,15, 20-tetrakis (4-carboxyphenyl) porphyrin, 1,3,5, 7-adamantanetetracarboxylic acid, 1, 2-diphenyl-1, 2-bis (4-carboxyphenyl) ethylene, 1,3, 5-tris (4-carboxyphenylethynyl) benzene, 1,3, 5-tris (4' -aminophenoxy) benzene, 1, 4-bis (2',6, ' -dicarboxyphenyl-4 ' -pyridine) benzene.
Preferably, in S2, the heat treatment is performed in a protective atmosphere, and the temperature of the heat treatment is 800-1200 ℃ for 2-10 h.
Preferably, in the heat treatment process, the temperature is raised to 800-1200 ℃ at the temperature raising rate of 1 ℃/min for heat treatment for 2-10 h.
Preferably, in S2, the method of the reaction is a solvothermal method or a seed crystal method or a microwave method.
Preferably, in S3, the molar concentration of zinc in the zinc salt solution is 0.10-0.35 mol/L; in the zinc salt solution, the zinc salt is one or a mixture of two of zinc nitrate and zinc chloride, and the solvent is one or a mixture of two of methanol and ethanol; the second organic ligand is 2-methylimidazole; the 2-methylimidazole is prepared into 0.5-2.0g/L alcoholic solution and added in an amount which is 1.0-2.5 times of the volume of the zinc salt solution.
Preferably, in S2, the MOFs-modified silicon-based precursor material in S2 is placed in a zinc salt solution in an amount of 30-50g/100 ml.
The invention also provides the MOFs modified silicon-based negative electrode material, which is prepared by adopting the preparation method of the MOFs modified silicon-based negative electrode material.
In the technical scheme of the invention, the conductivity is greatly improved by introducing the reticular MOFs structure and taking carbon as the silicon cathode material of the network framework, and the alloying can effectively avoid the problem of serious volume expansion generated by conventional alloying and realize the organic matching of the silicon base material and metal. Meanwhile, after the MOFs particles of silver and/or manganese and/or iron are introduced for modification, the conductivity and electrochemical performance of the silicon-based negative electrode material can be greatly improved, and the rate capability and the cycle performance of the silicon-based negative electrode material are remarkably improved. Furthermore, according to the technical scheme of the invention, MOFs particles are secondarily modified on the formed granular silicon MOFs carrier, so that the silicon-based negative electrode material has certain hydrophobicity, the dispersibility of the silicon-based negative electrode material can be obviously improved, and when the silicon-carbon negative electrode material is used for preparing the silicon-carbon negative electrode material, a gap core-shell structure can be effectively formed, namely, the core-shell structure is separated and does not contact with each other, so that the adverse effect caused by the volume expansion of silicon is reduced.
The invention has the advantages that:
1) through technical improvement, the problem of huge volume expansion generated in the alloying process of the silicon-based negative electrode material is avoided, and the structural stability of the alloyed silicon-based negative electrode material is improved;
2) the conductive performance of the silicon-based negative electrode material can be remarkably improved and enhanced by introducing the alloy element and the carbon skeleton, and the electrochemical performance of the silicon-based negative electrode material can be improved after the metal ions are reasonably doped;
3) the dispersibility of the silicon-based negative electrode material is improved through hydrophobic modification so as to reduce the volume expansion hazard of the silicon-carbon negative electrode material;
4) the multiplying power performance and the cycle performance of the whole silicon-based negative electrode material in actual use are obviously improved.
Drawings
FIG. 1 is a comparative graph of the room temperature 100mA cycle discharge capacity curve of the battery prepared by the silicon-based anode materials prepared in the example 2 and the comparative example 2 of the present invention;
fig. 2 is a graph comparing discharge capacity curves of batteries manufactured by using silicon-based negative electrode materials prepared in example 2 of the present invention and comparative example 2 under different rate conditions.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
A MOFs modified silicon-based negative electrode material is prepared by the following method:
1) respectively preparing 0.2mol/L ethyl orthosilicate ether solution and 0.1mol/L silver nitrate acetone solution, and mixing in equal volumes to obtain precursor liquid;
2) adding 1,3, 5-tris (4-carboxyphenylethynyl) benzene into the precursor liquid in a proportion of 0.04mol per liter, carrying out MOFs modification through a solvothermal reaction at 200 ℃ for 10h, and heating to 800 ℃ at a heating rate of 1 ℃/min under the protection of nitrogen after drying a coating plate at 80 ℃ for 10h to obtain a MOFs modified silicon-based precursor material;
3) mixing 50g of MOFs modified silicon-based precursor material: 100mL of the solution is placed in 0.15mol/L zinc nitrate ethanol solution, 1.5L of 2-methylimidazole ethanol solution with the concentration of 1.0g/L is added into each liter of the zinc nitrate ethanol solution, the solution is added in three times in an equivalent manner in the adding process, the solution is mixed and reacted for 4 hours after each addition, solid is filtered after the addition and the reaction are completed, and the solid is subjected to heat treatment at 60 ℃ for 12 hours and dried to obtain the MOFs modified silicon-based negative electrode material.
Example 2
A silicon-based anode material modified by MOFs is prepared by the following method:
1) respectively preparing 0.75mol/L silicon tetrachloride petroleum ether solution and 0.375mol/L ferric chloride hexahydrate propyl acetate solution, and mixing in equal volumes to obtain precursor liquid;
2) adding 1,3, 5-tris (4-carboxyphenylethynyl) benzene into the precursor liquid in a proportion of 0.25mol per liter, carrying out MOFs modification through a solvothermal reaction at 200 ℃ for 12h, heating to 1000 ℃ at a heating rate of 1 ℃/min after drying a coating plate at 80 ℃ under the protection of nitrogen, and carrying out heat treatment for 8h to obtain a MOFs modified silicon-based precursor material;
3) mixing 50g of MOFs modified silicon-based precursor material: 100mL of the solution is placed in 0.30mol/L zinc nitrate ethanol solution, 2.0L of 2-methylimidazole ethanol solution with the concentration of 1.5g/L is added into each liter of zinc nitrate ethanol solution, in the adding process, the solution is added in three times in equal amount, the materials are mixed and reacted for 4 hours after each addition, solid is filtered after the addition and the reaction are completed, and the solid is subjected to heat treatment at 60 ℃ for 12 hours and dried to obtain the MOFs modified silicon-based negative electrode material.
Example 3
A silicon-based anode material modified by MOFs is prepared by the following method:
1) respectively preparing 1.0mol/L silicon tetrachloride chloroform solution and 0.5mol/L methyl acetate solution of manganese sulfate, and mixing in equal volume to obtain precursor liquid;
2) adding 1, 4-bis (2',6, ' -dicarboxyphenyl-4 ' -pyridine) benzene into the precursor liquid in a proportion of 0.3mol per liter, carrying out MOFs modification through a solvothermal reaction at 200 ℃ for 14h, heating to 1000 ℃ at a heating rate of 1 ℃/min under the protection of nitrogen after a coating plate at 80 ℃ is dried, and carrying out heat treatment for 6.5h to obtain a MOFs modified silicon-based precursor material;
3) mixing 30g of MOFs modified silicon-based precursor material: 100mL of the solution is placed in 0.1mol/L zinc nitrate ethanol solution, 1.0L of 2-methylimidazole ethanol solution with the concentration of 2.0g/L is added into each liter of zinc nitrate ethanol solution, the solution is added in three times in an equivalent manner in the adding process, the materials are mixed and reacted for 4 hours after each addition, a solid is filtered after the addition and the reaction are completed, and the solid is subjected to heat treatment at 60 ℃ for 12 hours and dried to obtain the MOFs modified silicon-based negative electrode material.
Example 4
A MOFs modified silicon-based negative electrode material is prepared by the following method:
1) respectively preparing 1.0mol/L ethyl orthosilicate ether solution and 1.0mol/L silver nitrate acetone solution, and mixing in equal volume to obtain precursor liquid;
2) adding 1,3, 5-tris (4-carboxyphenylethynyl) benzene into the precursor liquid in a proportion of 0.5mol per liter, carrying out MOFs modification through a solvothermal reaction at 200 ℃ for 14h, drying a coated plate at 80 ℃, and then heating to 1000 ℃ at a heating rate of 1 ℃/min under the protection of nitrogen for heat treatment for 9h to obtain a MOFs modified silicon-based precursor material;
3) mixing 50g of MOFs modified silicon-based precursor material: 100mL of the solution is placed in 0.35mol/L zinc nitrate ethanol solution, 2.5L of 2-methylimidazole ethanol solution with the concentration of 1.5g/L is added into each liter of the zinc nitrate ethanol solution, the solution is added in three times in an equivalent manner in the adding process, the solution is mixed and reacted for 4 hours after each addition, solid substances are filtered after the addition and the reaction are completed, and the solid substances are subjected to heat treatment at 60 ℃ for 12 hours and dried to obtain the MOFs modified silicon-based negative electrode material.
Example 5
A MOFs modified silicon-based negative electrode material is prepared by the following method:
1) respectively preparing 0.1mol/L ethyl orthosilicate ether solution and 0.2mol/L silver nitrate acetone solution, and mixing in equal volumes to obtain precursor liquid;
2) adding 1,3, 5-tris (4-carboxyphenylethynyl) benzene into the precursor liquid in a proportion of 0.05mol per liter, carrying out MOFs modification through a solvothermal reaction at 200 ℃ for 14h, heating to 1200 ℃ at a heating rate of 1 ℃/min under the protection of nitrogen after drying a coating plate at 80 ℃, and carrying out heat treatment for 2h to obtain the MOFs modified silicon-based precursor material;
3) mixing 50g of MOFs modified silicon-based precursor material: 100mL of the solution is placed in 0.35mol/L zinc chloride ethanol solution, 2.4L of 2-methylimidazole ethanol solution with the concentration of 0.5g/L is added into each liter of the zinc chloride ethanol solution, the solution is added in three times in equal amount in the adding process, the solution is mixed and reacted for 4 hours after each addition, solid substances are filtered after the addition and the reaction are completed, and the solid substances are subjected to heat treatment at 60 ℃ for 12 hours and dried to obtain the MOFs modified silicon-based negative electrode material.
Example 6
A silicon-based anode material modified by MOFs is prepared by the following method:
1) respectively preparing 0.1mol/L trichlorosilane ethyl ether solution and 0.1mol/L silver chloride pyridine solution, and mixing in equal volumes to obtain precursor liquid;
2) adding 5, 15-di (4' -carboxyphenyl) porphyrin into the precursor liquid according to the proportion of 0.0125mol per liter, carrying out MOFs modification through a solvothermal reaction at 200 ℃ for 12h, heating to 1100 ℃ at the heating rate of 1 ℃/min under the protection of nitrogen after drying a coating plate at 80 ℃, and carrying out heat treatment for 5.5h to obtain the MOFs modified silicon-based precursor material;
3) mixing 50g of MOFs modified silicon-based precursor material: putting 100mL of the solution into 0.17mol/L zinc chloride ethanol solution, adding 0.8 g/L2-methylimidazole ethanol solution into the zinc chloride ethanol solution for three times, adding 0.8L of zinc chloride ethanol solution per liter in the adding process, mixing and reacting for 3 hours after each addition, filtering out solids after the addition and the reaction are completed, and performing heat treatment on the solids at 70 ℃ for 10 hours to obtain the MOFs modified silicon-based negative electrode material.
Example 7
A MOFs modified silicon-based negative electrode material is prepared by the following method:
1) respectively preparing 0.2mol/L of benzene and petroleum ether solution of ethyl orthosilicate and 0.1mol/L of silver nitrate acetone solution, and mixing in equal volume to obtain precursor liquid;
2) adding 1,3, 5-tris (4-carboxyphenylethynyl) benzene into the precursor liquid in a proportion of 0.04mol per liter, carrying out MOFs modification through a solvothermal reaction at 200 ℃ for 10h, and heating to 800 ℃ at a heating rate of 1 ℃/min under the protection of nitrogen after drying a coating plate at 80 ℃ for 10h to obtain a MOFs modified silicon-based precursor material;
3) mixing 50g of MOFs modified silicon-based precursor material: 100mL of the solution is placed in 0.15mol/L zinc nitrate ethanol solution, 1.5L of 2-methylimidazole ethanol solution with the concentration of 1.0g/L is added into each liter of the zinc nitrate ethanol solution, the solution is added in three times in an equivalent manner in the adding process, the solution is mixed and reacted for 4 hours after each addition, solid is filtered after the addition and the reaction are completed, and the solid is subjected to heat treatment at 60 ℃ for 12 hours and dried to obtain the MOFs modified silicon-based negative electrode material.
Example 8
A silicon-based anode material modified by MOFs is prepared by the following method:
1) respectively preparing 0.2mol/L ethyl orthosilicate ether solution and 0.1mol/L silver nitrate toluene and ether solution, and mixing in equal volume to obtain precursor liquid;
2) adding 1,3, 5-tris (4-carboxyphenylethynyl) benzene into the precursor liquid in a proportion of 0.04mol per liter, carrying out MOFs modification through a solvothermal reaction at 200 ℃ for 10h, and heating to 800 ℃ at a heating rate of 1 ℃/min under the protection of nitrogen after drying a coating plate at 80 ℃ for 10h to obtain a MOFs modified silicon-based precursor material;
3) mixing 50g of MOFs modified silicon-based precursor material: 100mL of the solution is placed in 0.15mol/L zinc nitrate ethanol solution, 1.5L of 2-methylimidazole ethanol solution with the concentration of 1.0g/L is added into each liter of the zinc nitrate ethanol solution, the solution is added in three times in an equivalent manner in the adding process, the solution is mixed and reacted for 4 hours after each addition, solid is filtered after the addition and the reaction are completed, and the solid is subjected to heat treatment at 60 ℃ for 12 hours and dried to obtain the MOFs modified silicon-based negative electrode material.
Comparative example 1
The specific procedure was the same as in example 2, except that: and 2) adding no first organic ligand to modify the MOFs particles.
Comparative example 2
Directly coating and drying 0.75mol/L silicon tetrachloride petroleum ether solution at the temperature of 80 ℃, and then carrying out heat treatment for 8 hours at the temperature of 1000 ℃ under the protection of nitrogen (the heating rate is 1 ℃/min) to obtain the silicon-based negative electrode material.
Comparative example 3
The specific procedure was the same as in example 2, except that: the treatment of the step 3) is not carried out, and the silicon-based precursor material modified by MOFs is directly used as the silicon-based cathode material.
Blank control group (CK group)
Silicon-based anode materials are commercially available.
And (3) testing:
the silicon-based negative electrode materials prepared in the above examples 1 to 8 and comparative examples 1 to 3 and commercially available silicon-based negative electrode materials were assembled into button cells. Mixing the obtained silicon-based negative electrode material, CMC-Na, SBR and SP in a mass ratio of 95:1.5:2:1.5, preparing the slurry into a negative electrode by a conventional process, taking a pure lithium sheet as a counter electrode, adopting a PE diaphragm with the thickness of 20 mu m in the middle, using an electrolyte active substance of 1mol/L LiPF6, using an electrolyte solvent in a volume ratio of EC: EMC of 1:1, adding a proper amount of foam nickel gasket according to the residual space of the button cell, and finally assembling the button cell with the model of CR2032 in a glove box filled with argon, wherein the serial number of the cell corresponds to the source of the silicon-based negative electrode material.
And (3) carrying out cycle performance and rate performance tests on the prepared CR2032 button cell.
Wherein, the comparative graph of the discharge capacity curve of 100mA cycles at normal temperature of the batteries prepared by the negative electrode materials of the example 2 and the comparative example 2 is shown in figure 1, and the comparative graph of the discharge capacity curve under the condition of different multiplying powers is shown in figure 2, wherein: silicon-MOFs refers to example 2, silicon refers to comparative example 2; as can be seen from fig. 1 and fig. 2, the dual MOFs-modified silicon-based anode material of the present invention is significantly superior to a silicon-based anode material without MOFs modification in both cycle performance and rate performance.
Specifically, the cycle performance and rate performance of each CR2032 button cell are shown in the following table
Wherein, the rate performance test is as follows: the cycles were performed in the order of 0.1C (100mA), 0.2C (200mA), 0.3C (300mA), 0.4C (400mA) and 0.5C (500mA) magnification, and 10 cycles (51-60 th cycles) were performed in the order of 0.1C (100 mA). In the table, the 0.5C rate cycle retention rate is the 50 th cycle capacity retention rate, and the rate tests 51 to 60 cycle capacity retention rates are the 60 th cycle capacity retention rates.
From the data in the table, it can be seen that, in the technical scheme of the invention, two times of MOFs particle modification have significant influence on the performance of the silicon-based negative electrode material. Relatively, the modification of the first MOFs particles is more excellent and remarkable for directly improving the conductivity and electrochemical performance of the silicon-based anode material, the comparative example 3 is better than the comparative example 1 in terms of 80% capacity normal-temperature cycle number and 0.5C multiplying power cycle retention rate, and the performance of the comparative example 1 is better than that of the comparative example 3 in terms of multiplying power test of 51-60 cycle capacity retention rate. Therefore, in fact, the main effect of Ag/Mn/Fe-MOFs particle modification is to improve the direct conductivity and the direct electrochemical performance of the silicon-based negative electrode material, and the purpose of Zn-MOFs particle modification is to improve the adaptability of the silicon-carbon negative electrode material formed by mixing the silicon-based negative electrode material and the carbon material to the multiplying power, and the capacity of the silicon-carbon negative electrode material can be quickly recovered by switching to low-multiplying-power circulation after high-multiplying-power circulation; moreover, the effect generated by the combination of the two is better than that generated by any one of the two, a certain synergistic effect is generated, and the performance improvement effect is obvious.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a MOFs modified silicon-based negative electrode material is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing a precursor liquid containing a silicon source and a metal salt;
s2, adding a first organic ligand into the precursor liquid in the S1 to react to perform MOFs modification, and carrying out heat treatment after coating and drying to obtain a MOFs modified silicon-based precursor material;
s3, placing the MOFs modified silicon-based precursor material in the S2 in a zinc salt solution, adding a second organic ligand for hydrophobic modification, and drying to obtain the MOFs modified silicon-based negative electrode material.
2. The method for preparing a MOFs-modified silicon-based negative electrode material according to claim 1, wherein: in S1, the silicon source includes one or more of trichlorosilane, silicon tetrachloride, ethyl orthosilicate, and sodium silicate; the metal salt comprises one or more of silver salt, manganese salt and ferric salt.
3. The method for preparing a MOFs-modified silicon-based negative electrode material according to claim 1 or 2, wherein: at S1, the metal salt includes one or more of silver nitrate, silver chloride, silver bromide, manganese chloride, manganese sulfate, manganese acetate, potassium permanganate, ferric chloride hexahydrate, ferric nitrate, and ferric sulfate.
4. The method for preparing a MOFs-modified silicon-based negative electrode material according to claim 1 or 2, wherein: in S1, dissolving a silicon source in a solvent A to obtain a silicon solution, and dissolving a metal salt in a solvent B to obtain a salt solution; mixing a silicon solution with a salt solution to obtain a precursor solution containing a silicon source and a metal salt; the A-type solvent comprises one or more of benzene, chloroform, diethyl ether and petroleum ether; the B-type solvent comprises one or more of benzene, toluene, pentane, hexane, cyclohexane, cyclohexanone, methylcyclohexanone, diethyl ether, epoxypropane, methyl acetate, ethyl acetate, propyl acetate, acetone, methyl butanone, methyl isobutyl ketone, ethylene glycol monomethyl ether, acetonitrile, pyridine and phenol.
5. The method for preparing MOFs-modified silicon-based negative electrode material according to claim 4, wherein: the molar concentration of the silicon element in the silicon solution is 0.1-1.0 mol/L; the molar concentration of metal ions in the salt solution is 0.1-1.0 mol/L; the molar ratio of silicon element to metal ion in the precursor liquid after the silicon solution and the salt solution are mixed is 1: 0.5-2.
6. The method for preparing a MOFs-modified silicon-based negative electrode material according to claim 1, wherein: in S2, the first organic ligand is one or a mixture of more of carboxylic acid organic ligands, ammonia organic ligands, and pyridine organic ligands; the molar usage of the first organic ligand is 0.125-0.5 times of the total molar weight of the silicon element and the metal ions in the precursor liquid in S1.
7. The preparation method of the MOFs-modified silicon-based anode material according to claim 1, wherein the preparation method comprises the following steps: the first organic ligand is one or a mixture of more of 5, 15-di (4' -carboxyphenyl) porphyrin, 1, 2-di (4-carboxyphenyl) -1, 2-stilbene, 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin, 1,3,5, 7-adamantanetetracarboxylic acid, 1, 2-diphenyl-1, 2-di (4-carboxyphenyl) ethylene, 1,3, 5-tri (4-carboxyphenylethynyl) benzene, 1,3, 5-tri (4' -aminophenoxy) benzene, 1, 4-bis (2',6, ' -dicarboxyphenyl-4 ' -pyridine) benzene.
8. The method for preparing a MOFs-modified silicon-based negative electrode material according to claim 1, wherein: in S2, the heat treatment is carried out in a protective atmosphere, and the temperature of the heat treatment is 800-1200 ℃ for 2-10 h.
9. The method for preparing a MOFs-modified silicon-based negative electrode material according to claim 1, wherein: in S3, the molar concentration of zinc in the zinc salt solution is 0.10-0.35 mol/L; in the zinc salt solution, the zinc salt is one or a mixture of two of zinc nitrate and zinc chloride, and the solvent is one or a mixture of two of methanol and ethanol; the second organic ligand is 2-methylimidazole; the 2-methylimidazole is prepared into 0.5-2.0g/L alcoholic solution and added in an amount which is 1.0-2.5 times of the volume of the zinc salt solution.
10. A MOFs modified silicon-based negative electrode material is characterized in that: the preparation method of the MOFs-modified silicon-based negative electrode material as claimed in any one of claims 1 to 9.
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| CN115536859A (en) * | 2022-11-30 | 2022-12-30 | 中山大学 | Porphyrin metal-organic framework material based on bimetallic oxygen chain and preparation method and application thereof |
| CN115986121A (en) * | 2022-12-29 | 2023-04-18 | 重庆太蓝新能源有限公司 | Silicon-based material and preparation method and application thereof |
| CN116387483A (en) * | 2023-03-31 | 2023-07-04 | 重庆太蓝新能源有限公司 | Si@C@MOFs composite material and preparation method thereof, negative electrode material, negative electrode plate and lithium battery |
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| CN116387483B (en) * | 2023-03-31 | 2024-04-02 | 重庆太蓝新能源有限公司 | Si@C@MOFs composite material and preparation method thereof, negative electrode material, negative electrode plate and lithium battery |
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