CN117673282A - Phosphorus-based negative electrode material, phosphorus-based composite electrode, and preparation method and application thereof - Google Patents
Phosphorus-based negative electrode material, phosphorus-based composite electrode, and preparation method and application thereof Download PDFInfo
- Publication number
- CN117673282A CN117673282A CN202211021144.6A CN202211021144A CN117673282A CN 117673282 A CN117673282 A CN 117673282A CN 202211021144 A CN202211021144 A CN 202211021144A CN 117673282 A CN117673282 A CN 117673282A
- Authority
- CN
- China
- Prior art keywords
- phosphorus
- oxide layer
- electrode
- lithium
- situ
- 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
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 502
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 407
- 239000011574 phosphorus Substances 0.000 title claims abstract description 407
- 239000002131 composite material Substances 0.000 title claims abstract description 138
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 238000011065 in-situ storage Methods 0.000 claims abstract description 152
- 238000003763 carbonization Methods 0.000 claims abstract description 109
- 239000011230 binding agent Substances 0.000 claims abstract description 101
- 239000000126 substance Substances 0.000 claims abstract description 81
- 239000003792 electrolyte Substances 0.000 claims abstract description 72
- 239000006185 dispersion Substances 0.000 claims abstract description 70
- 239000005416 organic matter Substances 0.000 claims abstract description 66
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 64
- 239000010405 anode material Substances 0.000 claims abstract description 62
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000001301 oxygen Substances 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000012298 atmosphere Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000011888 foil Substances 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 148
- 230000003647 oxidation Effects 0.000 claims description 117
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 85
- 229910001416 lithium ion Inorganic materials 0.000 claims description 85
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 72
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 59
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 56
- 239000007788 liquid Substances 0.000 claims description 51
- 239000006258 conductive agent Substances 0.000 claims description 50
- 239000011162 core material Substances 0.000 claims description 47
- 239000011248 coating agent Substances 0.000 claims description 44
- 238000000576 coating method Methods 0.000 claims description 44
- 239000002033 PVDF binder Substances 0.000 claims description 38
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 30
- 229910052744 lithium Inorganic materials 0.000 claims description 30
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 27
- 229910001414 potassium ion Inorganic materials 0.000 claims description 27
- 229910001415 sodium ion Inorganic materials 0.000 claims description 26
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 23
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 21
- -1 polytetrafluoroethylene Polymers 0.000 claims description 21
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 229920002125 Sokalan® Polymers 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 14
- 239000004584 polyacrylic acid Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000003822 epoxy resin Substances 0.000 claims description 13
- 229920000647 polyepoxide Polymers 0.000 claims description 13
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007774 positive electrode material Substances 0.000 claims description 12
- 229960003351 prussian blue Drugs 0.000 claims description 12
- 239000013225 prussian blue Substances 0.000 claims description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 11
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 9
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- 229920005549 butyl rubber Polymers 0.000 claims description 8
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 8
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011368 organic material Substances 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 7
- 239000003273 ketjen black Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 150000002825 nitriles Chemical class 0.000 claims description 7
- 125000004437 phosphorous atom Chemical group 0.000 claims description 7
- 150000003457 sulfones Chemical class 0.000 claims description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000004146 energy storage Methods 0.000 claims description 6
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical group O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 4
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 claims description 4
- HIDOPYNXWKECHK-UHFFFAOYSA-L P(=O)([O-])([O-])F.[Fe+2].[Na+] Chemical compound P(=O)([O-])([O-])F.[Fe+2].[Na+] HIDOPYNXWKECHK-UHFFFAOYSA-L 0.000 claims description 4
- CHQMXRZLCYKOFO-UHFFFAOYSA-H P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F Chemical compound P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F CHQMXRZLCYKOFO-UHFFFAOYSA-H 0.000 claims description 4
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 claims description 4
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 claims description 4
- XLCPLIJTRIGVDU-UHFFFAOYSA-N [O-2].[Mn+2].[Ni+2].[Na+] Chemical compound [O-2].[Mn+2].[Ni+2].[Na+] XLCPLIJTRIGVDU-UHFFFAOYSA-N 0.000 claims description 4
- WSKOARFZINZCTI-UHFFFAOYSA-H [V+5].P(=O)([O-])([O-])[O-].[K+].P(=O)([O-])([O-])[O-] Chemical compound [V+5].P(=O)([O-])([O-])[O-].[K+].P(=O)([O-])([O-])[O-] WSKOARFZINZCTI-UHFFFAOYSA-H 0.000 claims description 4
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 4
- 150000004645 aluminates Chemical class 0.000 claims description 4
- 150000001721 carbon Chemical group 0.000 claims description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 4
- OBTSLRFPKIKXSZ-UHFFFAOYSA-N lithium potassium Chemical compound [Li].[K] OBTSLRFPKIKXSZ-UHFFFAOYSA-N 0.000 claims description 4
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 claims description 4
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 claims description 4
- YPPMLCHGJUMYPZ-UHFFFAOYSA-L sodium;iron(2+);sulfate Chemical compound [Na+].[Fe+2].[O-]S([O-])(=O)=O YPPMLCHGJUMYPZ-UHFFFAOYSA-L 0.000 claims description 4
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical group N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 229920006350 polyacrylonitrile resin Polymers 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 14
- 239000000243 solution Substances 0.000 claims 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims 1
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 238000010000 carbonizing Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 275
- 238000012360 testing method Methods 0.000 description 108
- 210000004027 cell Anatomy 0.000 description 73
- 238000000498 ball milling Methods 0.000 description 56
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 54
- 239000011267 electrode slurry Substances 0.000 description 51
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 27
- 229910052786 argon Inorganic materials 0.000 description 27
- 239000011889 copper foil Substances 0.000 description 27
- 238000001291 vacuum drying Methods 0.000 description 25
- 239000000843 powder Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000006229 carbon black Substances 0.000 description 19
- 230000008569 process Effects 0.000 description 19
- 230000001276 controlling effect Effects 0.000 description 17
- 238000005520 cutting process Methods 0.000 description 16
- 238000005303 weighing Methods 0.000 description 15
- 238000004806 packaging method and process Methods 0.000 description 14
- 230000004913 activation Effects 0.000 description 13
- 238000003760 magnetic stirring Methods 0.000 description 11
- 239000004743 Polypropylene Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- 239000007772 electrode material Substances 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- 229910013872 LiPF Inorganic materials 0.000 description 6
- 101150058243 Lipf gene Proteins 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- KGQGQFUYXIQQEV-UHFFFAOYSA-N 1,2-dimethoxyethane;thiolane 1,1-dioxide Chemical compound COCCOC.O=S1(=O)CCCC1 KGQGQFUYXIQQEV-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 208000031509 superficial epidermolytic ichthyosis Diseases 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of battery materials, and relates to a phosphorus-based negative electrode material, a phosphorus-based composite electrode, a preparation method and application thereof. Wherein the phosphorus-based anode material comprises a phosphorus simple substance core body and an oxide layer P generated on the surface of the core body in situ x O y And a carbonization layer; the preparation method comprises the following steps: oxygen generation by placing elemental phosphorus in an atmosphere containing oxygenAnd carbonizing the organic matter for the binder and the organic matter for the dispersion to obtain the phosphorus-based anode material with the oxide layer and the carbonized layer on the surface. In addition, the phosphorus-based composite electrode is prepared by oxidizing a metal foil containing a phosphorus element in an atmosphere containing oxygen and carbonizing an organic matter for electrolyte to obtain a phosphorus-based negative electrode with an oxide layer and a carbonized layer on the surface. The phosphorus-based negative electrode material and the phosphorus-based composite electrode prepared by the method remarkably improve the cycle stability and high-rate performance of the battery and prolong the storage time in the air. The preparation method provided by the invention is simple to operate and low in processing cost, and is considered as a method for hopefully realizing industrial production.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a phosphorus-based negative electrode material, a phosphorus-based composite electrode, a preparation method and application thereof.
Background
Secondary batteries are one of the most promising energy storage devices, playing an important role in electric vehicles, portable electronic products, and large-scale energy storage technologies. The development of high-capacity and high-safety negative electrode materials is a key for improving the performance of secondary batteries such as lithium/sodium/potassium ion batteries. For lithium ion batteries, the most commonly used negative electrode material is graphite, however, which is based on intercalation/deintercalation mechanisms, such that one lithium ion intercalates with six carbon atoms (forming lics 6 ) Can only provide a lower theoretical specific capacity (372 mAh.g -1 ). The alloyed negative electrode such as silicon is a negative electrode material with high theoretical specific capacity, which can realize the effect of each silicon atom with 4.4 lithium ions (forming Li 4.4 Si) to obtain a higher theoretical specific capacity (4200 mAh.g) -1 ). However, the silicon negative electrode has a low lithiation potential (0.2V vs Li + Li) is very close to the deposition potential of metallic lithium, which inevitably leads to severe dendrite growth during fast charging, leading to safety problems. In addition, graphite and silicon have sodium/potassium storage capacities that are too low to be commercially viable. Phase (C) In contrast, phosphorus is used as another alloying anode material, has higher theoretical specific capacity (2596 mAh.g -1 ) A safer lithiation potential (0.7V vs Li + Li) is considered to be an ideal negative electrode material having high energy density and fast charge capability. Meanwhile, the phosphorus anode also has higher sodium/potassium storage capacity of 2596 mAh.g respectively -1 (Na 3 P) and 865 mAh.g -1 (KP). In addition, the low cost and natural abundance of phosphorus also makes it suitable as a commercial negative electrode material for secondary batteries. However, the practical application of the phosphorus cathode also faces the great challenges, including large volume change (about 300 percent) in the charge and discharge process and low electronic conductivity (about 10-14S cm) -1 ) And unstable solid electrolyte layers (SEIs). The current common modification strategy is to compound the phosphorus anode with the carbon carrier or coat the phosphorus anode with the conductive polymer, and the like, and the volume expansion can be relieved and the conductivity can be improved to a certain extent, but the complex preparation process and the high cost and other factors make the phosphorus anode difficult to industrialize.
Disclosure of Invention
The technical problems solved by the invention are as follows: the modification strategy commonly used in the prior art is to compound the phosphorus anode with a carbon carrier or coat the phosphorus anode with a conductive polymer, and the like, and the volume expansion can be relieved and the conductivity can be improved to a certain extent, but the complex preparation process and the high cost and other factors make the phosphorus anode difficult to industrialize.
Aiming at the technical problems, the invention aims to provide a phosphorus-based negative electrode material, a phosphorus-based composite electrode, a preparation method and application thereof.
Specifically, the invention provides the following technical scheme:
in a first aspect, the invention provides a phosphorus-based anode material comprising a phosphorus core, an in-situ generated oxide layer on the surface of the phosphorus core and an in-situ generated carbonized layer; the in situ generated oxide layer contains P x O y X is more than 0 and less than or equal to 2, and y is more than 0 and less than or equal to 5; the oxidation degree is 10-70% in terms of oxygen content, wherein the oxygen content refers to the mass percentage of oxygen atoms relative to the total mass of oxygen atoms and phosphorus atoms in the phosphorus core material with the surface containing the in-situ generated oxide layer; the in situ generatedThe carbonization layer is a partially carbonized organic matter; the carbonization degree is 5% -50%, wherein the carbonization degree refers to the mass percentage of the mass of the carbonized carbon of the organic matters to the mass of the original phosphorus core.
In some embodiments, the degree of oxidation is from 35% to 50%.
In some embodiments, the degree of carbonization is 30% to 45%.
In some embodiments, the phosphorus core is elemental phosphorus.
In some embodiments, the elemental phosphorus contains one or more of red phosphorus, black phosphorus, violet phosphorus, blue phosphorus, green phosphorus, and fibrous phosphorus.
In some embodiments, the organic is selected from the group consisting of an organic for a binder and/or an organic for a dispersion.
In some embodiments, the binder organic matter comprises one or more of polyvinylidene fluoride, styrene-butadiene rubber, polytetrafluoroethylene, butyl rubber, epoxy resin, polyacrylic acid, polyacrylonitrile, polyimide, and polyethyleneimine.
In some embodiments, the organic matter for the binder is selected from one or more of butyl rubber, polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid, styrene-butadiene rubber, polyacrylonitrile, and epoxy resin.
In some embodiments, the binder organics are selected from one or more of styrene butadiene rubber, polyacrylic acid, and/or epoxy resin.
In some embodiments, the organic matter for the dispersion contains one or more of N-methylpyrrolidone, dimethylacetamide, dimethylformamide, N-methylpyrrole, dimethylsulfoxide, acetone, tetrahydrofuran, dimethylether, ethanol, and acetonitrile.
In some embodiments, the organic for the dispersion is selected from one or more of N-methylpyrrolidone, dimethylformamide, N-methylpyrrole, ethanol, dimethylsulfoxide, and acetone.
In some embodiments, the organic matter for the dispersion is selected from one or more of N-methylpyrrolidone, ethanol, and dimethylacetamide.
In a second aspect, the invention provides a method for preparing a phosphorus-based anode material, comprising the following steps:
(1) Placing the phosphorus core material in an atmosphere containing oxygen for oxidation reaction, and generating an oxide layer on the surface of the phosphorus core material in situ to obtain a phosphorus-based material with the oxide layer on the surface;
(2) And (3) placing the phosphorus-based material containing the oxide layer obtained in the step (1) in an organic matter for a binder and an organic matter for dispersion liquid for in-situ carbonization reaction to obtain the phosphorus-based anode material containing the oxide layer and the carbonized layer on the surface.
In some embodiments, in step (1), the particle size of the phosphorus core material is from 10nm to 50 μm.
In some embodiments, in step (1), the particle size of the phosphorus core material is 100nm to 1 μm.
In some embodiments, in step (1), the particle size of the phosphorus core material is from 100nm to 800nm.
In some embodiments, in step (1), the oxidizing is performed by placing the phosphorus core material in an atmosphere containing oxygen for a period of time t, wherein the period of time t is from 0.5 to 15 days.
In some embodiments, in step (1), the time t is 3 to 15 days.
In some embodiments, in step (1), the time t is between 5 and 15 days.
In some embodiments, in step (1), the time t is 8 to 15 days.
In some embodiments, in step (1), the temperature of the oxidation reaction is from 10 to 90 ℃.
In some embodiments, in step (1), the temperature of the oxidation reaction is from 10 to 40 ℃.
In some embodiments, in step (1), the volume fraction V of oxygen in the oxygen-containing atmosphere is from 5% to 100%.
In some embodiments, in step (1), the volume fraction V of oxygen in the oxygen-containing atmosphere is 15% to 98%.
In some embodiments, in step (1), the volume fraction V of oxygen in the oxygen-containing atmosphere is 21% to 95%.
In some embodiments, in step (1), the relative humidity RH of the oxidation reaction is from 0 to 50%, and does not comprise 0.
In some embodiments, in step (1), the relative humidity RH of the oxidation reaction is between 2% and 40%.
In some embodiments, in step (1), the relative humidity RH of the oxidation reaction is between 5% and 30%.
In some embodiments, in step (1), the relative humidity RH of the oxidation reaction is between 5% and 18%.
In some embodiments, in step (2), the carbonization reaction time t is from 5 minutes to 24 hours.
In some embodiments, in step (2), the carbonization reaction temperature T is 10 to 90 ℃.
In some embodiments, in step (2), the temperature T of the carbonization reaction is 25 to 80 ℃.
In some embodiments, in step (2), the temperature of the carbonization reaction is 60 to 80 ℃.
In some embodiments, in step (2), the binder organic matter is first dispersed in the dispersion organic matter to prepare a solution with the mass percentage of the binder organic matter being 1% -15%; and (2) adding the phosphorus-based anode material containing the oxide layer and the conductive agent obtained in the step (1) to perform in-situ carbonization reaction.
In some embodiments, in step (2), the binder organic matter is first dispersed in the dispersion organic matter to prepare a solution with the mass percentage of the binder organic matter being 1% -8%; and (2) adding the phosphorus-based anode material containing the oxide layer and the conductive agent obtained in the step (1) to perform in-situ carbonization reaction.
In some embodiments, in step (2), the sum of the mass percentages of the phosphorus-based negative electrode material containing the oxide layer, the conductive agent, and the binder organic matter is 100%.
In some embodiments, in the step (2), the mass percentage of the phosphorus-based anode material containing the oxide layer is 60% -95%, the mass percentage of the conductive agent is 2.5% -20%, and the mass percentage of the binder organic matter is 2.5% -20%.
In some embodiments, in step (2), the organic matter for the binder contains one or more of polyvinylidene fluoride, styrene-butadiene rubber, polytetrafluoroethylene, butyl rubber, epoxy resin, polyacrylic acid, polyacrylonitrile, polyimide, and polyethyleneimine.
In some embodiments, in step (2), the organic matter for the binder is selected from one or more of butyl rubber, polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid, styrene-butadiene rubber, polyacrylonitrile, and epoxy resin.
In some embodiments, in step (2), the organic matter for the binder is selected from one or more of polyvinylidene fluoride, styrene-butadiene rubber, polyacrylic acid, and epoxy resin.
In some embodiments, in step (2), the organic matter for the dispersion is selected from one or more of N-methylpyrrolidone, dimethylacetamide, dimethylformamide, N-methylpyrrole, dimethylsulfoxide, acetone, tetrahydrofuran, dimethylether, ethanol, and acetonitrile.
In some embodiments, in step (2), the organic matter for the dispersion is selected from one or more of N-methylpyrrolidone, dimethylformamide, N-methylpyrrole, ethanol, dimethylsulfoxide, and acetone.
In some embodiments, in step (2), the organic matter for the dispersion is selected from one or more of N-methylpyrrolidone, ethanol, and dimethylacetamide.
In some embodiments, a phosphorus-based anode material is prepared by the method of preparing a phosphorus-based anode material described above.
In some embodiments, a phosphorus-based composite electrode comprises the phosphorus-based negative electrode material described above.
In some embodiments, a lithium ion battery comprises the phosphorus-based composite electrode and an electrolyte.
In some embodiments, the positive electrode material in the lithium ion battery is selected from one or a combination of two or more of lithium cobaltate, lithium nickelate, lithium manganate, lithium nickelate aluminate, lithium manganate, lithium iron phosphate, lithium cobalt phosphate, lithium manganese phosphate, lithium vanadium phosphate and Prussian blue in any proportion.
In some embodiments, a sodium ion battery comprises the phosphorus-based composite electrode and an electrolyte.
In some embodiments, the positive electrode material in the sodium ion battery is selected from one or a combination of two or more of sodium nickel manganese oxide, sodium iron sulfate, sodium iron phosphate, sodium iron fluorophosphate, sodium vanadium phosphate, sodium vanadium fluorophosphate and Prussian blue in any proportion.
In some embodiments, a potassium ion battery comprises the phosphorus-based composite electrode and an electrolyte.
In some embodiments, the positive electrode material in the potassium ion battery is selected from one or a combination of two or more of lithium potassium cobaltate, potassium manganate, vanadium potassium phosphate and Prussian blue in any proportion.
In some embodiments, the lithium ion battery, sodium ion battery or potassium ion battery is used in the energy field.
In some embodiments, the lithium ion battery, sodium ion battery or potassium ion battery is used in the fields of electric vehicles, mobile power sources and energy storage power stations.
In a third aspect, the invention provides a phosphorus-based composite electrode, which is a phosphorus-based negative electrode with an in-situ generated oxide layer and an in-situ generated carbonized layer on the surface; the in situ generated oxide layer contains P x O y X is more than 0 and less than or equal to 2, and y is more than 0 and less than or equal to 5; the oxidation degree is 5 to 50% in terms of oxygen content, wherein the oxygen content refers to a mass percentage of oxygen atoms relative to the total mass of oxygen atoms, phosphorus atoms and carbon atoms; this isThe carbon atoms refer to carbon atoms in the carbon material which is not subjected to in-situ carbonization and serves as a conductive agent and is contained in the phosphorus-based negative electrode; the in-situ generated carbonization layer is a partially carbonized organic matter.
In some embodiments, the organic is selected from electrolyte organics.
In some embodiments, the electrolyte organic matter is selected from one or more of esters, ethers, sulfones, and nitriles solvents.
In some embodiments, the ester solvent is one or more of ethylene carbonate, diethyl carbonate, polycarbonate, dimethyl carbonate, methylethyl carbonate, propylene carbonate, ethyl chlorocarbonate, ethyl propionate, and propyl propionate.
In some embodiments, the ether solvent is one or more of ethylene glycol dimethyl ether, 1, 3-dioxolane, and diethylene glycol dimethyl ether.
In some embodiments, the sulfone-based solvent is sulfolane and/or dimethyl sulfoxide.
In some embodiments, the nitrile solvent is succinonitrile and/or adiponitrile.
In some embodiments, the electrolyte organic material is ethylene carbonate, diethyl carbonate, ethylene glycol dimethyl ether and/or dimethyl sulfoxide.
In a fourth aspect, the present invention provides a method for preparing a phosphorus-based composite electrode, comprising the steps of:
(1) Uniformly mixing a phosphorus core material, a conductive agent and a binder, adding a dispersion liquid, uniformly mixing, coating on the surface of a metal foil, and drying to obtain a phosphorus-based negative electrode;
(2) Placing the phosphorus-based negative electrode obtained in the step (1) in an atmosphere containing oxygen for oxidation reaction, and generating an oxide layer on the surface of the phosphorus-based negative electrode in situ to obtain the phosphorus-based negative electrode with the surface containing the oxide layer;
(3) And (3) placing the phosphorus-based negative electrode with the surface containing the oxide layer obtained in the step (2) into an electrolyte organic matter for in-situ carbonization reaction to obtain the phosphorus-based composite electrode.
In some embodiments, in step (1), the phosphorus core material is elemental phosphorus.
In some embodiments, the elemental phosphorus is selected from one or more of red phosphorus, black phosphorus, violet phosphorus, blue phosphorus, green phosphorus, and fibrous phosphorus.
In some embodiments, in step (1), the particle size of the phosphorus core material is from 10nm to 50 μm.
In some embodiments, in step (1), the particle size of the phosphorus core material is 100nm to 1 μm.
In some embodiments, in step (1), the particle size of the phosphorus core material is 300nm to 800nm.
In some embodiments, in step (1), the conductive agent is selected from one or more of carbon black, acetylene black, graphite, graphene, carbon nanotubes, porous carbon, ketjen black, carbon fiber, amorphous carbon, carbon nano/microspheres, and pitch-cracked carbon.
In some embodiments, in step (1), the binder is selected from one or more of polyvinylidene fluoride, styrene-butadiene rubber, polytetrafluoroethylene, butyl rubber, epoxy resin, polyacrylic acid, polyacrylonitrile, polyimide, and polyethyleneimine.
In some embodiments, in step (1), the dispersion is prepared with a solvent comprising one or more of N-methylpyrrolidone, dimethylacetamide, dimethylformamide, N-methylpyrrole, dimethylsulfoxide, acetone, tetrahydrofuran, dimethylether, ethanol, and acetonitrile.
In some embodiments, in step (1), the metal foil is copper foil.
In some embodiments, in step (2), the oxidizing is performed by placing the phosphorus core material in an atmosphere containing oxygen for a period of time t, where the period of time t is: and 0.5 to 15 days.
In some embodiments, in step (2), the time t of placement is: 2-15 days.
In some embodiments, in step (2), the time t of placement is: 7-15 days.
In some embodiments, in step (2), the time t of placement is: and 10-15 days.
In some embodiments, in step (2), the temperature of the oxidation reaction is from 10 to 90 ℃.
In some embodiments, in step (2), the temperature of the oxidation reaction is from 10 to 40 ℃.
In some embodiments, in step (2), the volume fraction V of oxygen in the oxygen-containing atmosphere is: 5% -100%.
In some embodiments, in step (2), the volume fraction V of oxygen in the oxygen-containing atmosphere is: 15% -98%.
In some embodiments, in step (2), the volume fraction V of oxygen in the oxygen-containing atmosphere is 21% to 95%.
In some embodiments, in step (2), the relative humidity RH of the oxidation reaction is: 0 to 50%, and excluding 0.
In some embodiments, in step (2), the relative humidity RH of the oxidation reaction is: 1 to 45 percent.
In some embodiments, in step (2), the relative humidity RH of the oxidation reaction is: 2% -30%.
In some embodiments, in step (2), the relative humidity RH of the oxidation reaction is: 10% -30%.
In some embodiments, in step (3), the carbonization reaction is performed for a time t of: and 5 min-24 h.
In some embodiments, in step (3), the carbonization reaction is performed for a time t of: 8 min-20 h.
In some embodiments, in step (3), the carbonization reaction is performed for a time t of: and the time is 10 min-12 h.
In some embodiments, in step (3), the temperature T of the carbonization reaction is 20 to 40 ℃.
In some embodiments, in step (3), the phosphorus-based negative electrode sheet obtained in step (2) having an oxide layer on the surface is placed in an electrolyte organic material to undergo carbonization reaction.
In some embodiments, in step (3), the weight of the phosphorus-based negative electrode material per square centimeter of metal foil is from 1 to 2mg.
In some embodiments, in step (3), the volume of the electrolyte organic substance corresponding to each mg of the phosphorus-based negative electrode material on the phosphorus-based negative electrode sheet is 50 to 300 μl.
In some embodiments, in step (3), the electrolyte organic matter is selected from one or more of esters, ethers, sulfones, and nitriles solvents.
In some embodiments, in step (3), the electrolyte organic matter is selected from one or more of esters, ethers, sulfones, and nitriles solvents.
In some embodiments, in step (3), the ester solvent is one or more of ethylene carbonate, diethyl carbonate, polycarbonate, dimethyl carbonate, methylethyl carbonate, propylene carbonate, ethyl chlorocarbonate, ethyl propionate, and propyl propionate.
In some embodiments, in step (3), the ether solvent is one or more of ethylene glycol dimethyl ether, 1, 3-dioxolane, and diethylene glycol dimethyl ether.
In some embodiments, in step (3), the sulfone-based solvent is sulfolane and/or dimethyl sulfoxide.
In some embodiments, in step (3), the nitrile solvent is succinonitrile and/or adiponitrile.
In some embodiments, in step (3), the electrolyte organic material is ethylene carbonate, dimethyl carbonate, dioxolane, ethylene glycol dimethyl ether sulfolane, and/or dimethyl sulfoxide.
In some embodiments, a phosphorus-based composite electrode is prepared by the method of preparing a phosphorus-based composite electrode described above.
In some embodiments, a lithium ion battery comprising the phosphorus-based composite electrode and an electrolyte; wherein the electrolyte and the electrolyte organic matter are selected from the same substances.
In some embodiments, the positive electrode material in the lithium ion battery is selected from one or a combination of two or more of lithium cobaltate, lithium nickelate, lithium manganate, lithium nickelate aluminate, lithium manganate, lithium iron phosphate, lithium cobalt phosphate, lithium manganese phosphate, lithium vanadium phosphate and Prussian blue in any proportion.
In some embodiments, a sodium ion battery comprising the phosphorus-based composite electrode and an electrolyte; wherein the electrolyte and the electrolyte organic matter are selected from the same substances.
In some embodiments, the positive electrode material in the sodium ion battery is selected from one or a combination of two or more of sodium nickel manganese oxide, sodium iron sulfate, sodium iron phosphate, sodium iron fluorophosphate, sodium vanadium phosphate, sodium vanadium fluorophosphate and Prussian blue in any proportion.
In some embodiments, a potassium ion battery comprising the phosphorus-based composite electrode of claim 21, 22, or 32 and an electrolyte; wherein the electrolyte and the electrolyte organic matter are selected from the same substances.
In some embodiments, the positive electrode material in the potassium ion battery is selected from one or a combination of two or more of lithium potassium cobaltate, potassium manganate, vanadium potassium phosphate and Prussian blue in any proportion.
In some embodiments, the lithium ion battery, sodium ion battery or potassium ion battery is used in the energy field;
in some embodiments, the lithium ion battery, sodium ion battery or potassium ion battery is used in the fields of electric vehicles, mobile power sources and energy storage power stations.
The beneficial effects of the invention are that
(1) The invention provides a phosphorus-based anode material with an in-situ generated oxide layer and an in-situ generated carbonized layer on the surface. An oxide layer is generated on the surface of the phosphorus core in situ by a powder oxidation method, and can carbonize organic matters for the binder and organic matters for the dispersion liquid to form a carbonize layer, so that the interface interaction between phosphorus particles, the binder and the electrolyte is improved. In addition, due to the existence of the surface carbonization layer, the electronic conductivity of the whole composite electrode can be improved, meanwhile, the carbonization layer can be used as a coating layer to relieve the volume expansion problem of the phosphorus-based composite electrode to a certain extent, and the cycle stability of the phosphorus-based composite electrode is obviously improved.
(2) The invention provides a phosphorus-based composite electrode with an in-situ generated oxide layer and an in-situ generated carbide layer on the surface, wherein the oxide layer is generated on the surface of an electrode slice containing a phosphorus active material by a pole piece oxidation method, the oxide layer can carbonize an organic matter for electrolyte to form the carbide layer, and the carbide layer also has the advantage of improving the overall electronic conductivity and the circulation stability of the composite electrode.
(3) The invention provides a phosphorus-based negative electrode material containing an in-situ generated oxide layer and a carbonization layer or a phosphorus-based composite electrode containing an in-situ generated oxide layer and an in-situ generated carbonization layer, wherein the oxide layer can induce generation of uniform lithium carbonate, lithium phosphide, lithium oxide, lithium fluoride and Li x PO y F z The solid electrolyte phase interface (SEI) of the material has higher ionic conductivity compared with SEI formed on the surface of fresh phosphorus particles, can realize faster reaction kinetics process, and further improves the high-rate performance of the phosphorus-based composite electrode.
(4) The phosphorus-based negative electrode material containing the in-situ generated oxide layer and the carbonization layer or the phosphorus-based composite electrode containing the in-situ generated oxide layer and the in-situ generated carbonization layer, provided by the invention, can be used as a protective layer, can be used for blocking air from contacting with phosphorus in the oxide layer, reduces the continuous oxidation of the phosphorus with activity in the inside, and prolongs the storage time of the phosphorus negative electrode in the air.
(5) The invention provides a preparation method of a phosphorus-based negative electrode material containing an in-situ generated oxide layer and an in-situ generated carbonized layer and a preparation method of a phosphorus-based composite electrode containing the in-situ generated oxide layer and the in-situ generated carbonized layer, and the preparation method has the advantages of simplicity in operation, low cost, no need of additional materials and processing cost and the like, and is considered to be a method for realizing industrial production.
Drawings
FIG. 1 shows NMP, P 2 O 5 NMP and P 2 O 5 Ultraviolet-visible absorption spectrum of the reaction product.
FIG. 2 is a STEM (b) and corresponding line scan of the product of (a) PVDF (NMP) carbonized by a phosphor core material BP-5 containing an oxide layer.
Fig. 3 is a scanning electron microscope image of the phosphorus-based anode material containing the in-situ generated oxide layer prepared in example 1.
Fig. 4 is a cyclic voltammogram of a lithium ion half cell assembled from the phosphorus negative electrode material containing an in-situ grown oxide layer and an in-situ grown carbide layer prepared in example 1.
Fig. 5 is a graph showing the rate performance of the batteries assembled from the phosphorus-based negative electrodes obtained in examples 1, 3, 5, and 6 and comparative example 2 at different current densities.
Fig. 6 is a graph showing the rate performance of the lithium ion half-cell obtained in example 8 and comparative example 9 at different current densities.
Fig. 7 is a graph showing the rate performance of the lithium ion half cell obtained in comparative example 12 at different current densities.
Detailed Description
As described above, the invention aims to provide a phosphorus-based negative electrode material, a phosphorus-based composite electrode, a preparation method and application thereof, and the technical problems of poor cycle stability, poor rate capability and the like of a phosphorus negative electrode in the prior art are solved.
In order to solve the technical problems of poor cycling stability, poor rate capability and the like of the phosphorus anode in the prior art. Through long-term researches and experiments, the applicant finds that the technical problems can be solved by forming an oxide layer on the surface of a phosphorus particle material and the surface of a phosphorus-based electrode taking phosphorus particles as active substances in situ and then forming a carbonized layer on the surface of the oxide layer in situ.
In order to solve the technical problems, the invention provides two technical schemes.
The first technical scheme provides a phosphorus-based anode material, which comprises a phosphorus core, an in-situ generated oxide layer and an in-situ generated carbonized layer; the in situ generated oxide layer contains P x O y X is more than 0 and less than or equal to 2, and y is more than 0 and less than or equal to 5; the oxidation degree is 10-70% in terms of oxygen content, wherein the oxygen content refers to the mass percentage of oxygen atoms relative to the total mass of oxygen atoms and phosphorus atoms in the phosphorus core material with the surface containing the in-situ generated oxide layer; the carbonization layer generated in situ is a partially carbonized organic matter; the carbonization degree is 5% -50%, wherein the carbonization degree refers to the mass percentage of the mass of the carbonized carbon of the organic matters to the mass of the original phosphorus core.
Wherein, the phosphorus-based negative electrode material comprises the following technical steps:
(1) Placing a phosphorus core material with the particle size of 10 nm-50 mu m under the condition that the volume fraction of oxygen is 5% -100%, placing for 0.5-15 days to perform oxidation reaction, wherein the temperature of the oxidation reaction is 10-90 ℃, the relative humidity of the oxidation reaction is 0-50%, and the phosphorus core material does not contain 0, and generating an oxide layer on the surface of the phosphorus core material in situ to obtain a phosphorus base material containing the oxide layer (called a powder oxidation method);
(2) And then placing the phosphorus-based material containing the oxide layer in an organic matter for a binder and an organic matter for dispersion liquid for in-situ carbonization reaction to obtain the phosphorus-based anode material with the oxide layer and the carbonized layer on the surface.
Preferably, the preparation method of the phosphorus core material comprises the following steps: ball milling is carried out on the phosphorus simple substance; wherein the rotation speed of the ball milling treatment is 200-1000 rpm, preferably 250-600 rpm; and/or the ball milling treatment time is 8-24 hours.
The second technical scheme provides a phosphorus-based composite electrode, which is a phosphorus-based negative electrode with an in-situ generated oxide layer and an in-situ generated carbonized layer on the surface; the in situ generated oxide layer contains P x O y X is more than 0 and less than or equal to 2, and y is more than 0 and less than or equal to 5; the oxidation degree is 5% -50%; the in-situ generated carbonization layer is a partially carbonized organic matter.
Wherein, the phosphorus-based composite electrode comprises the following technical steps:
(1) Uniformly mixing a phosphorus core material with the particle size of 10 nm-50 mu m, a conductive agent and a binder, adding a dispersion liquid, uniformly mixing, coating on the surface of a metal foil, and drying to obtain a phosphorus-based negative electrode;
(2) Placing the phosphorus-based negative electrode obtained in the step (1) in an atmosphere containing oxygen for oxidation reaction, and generating an oxide layer on the surface of the phosphorus-based negative electrode in situ to obtain a phosphorus-based negative electrode with the surface containing the oxide layer (called a pole piece oxidation method); wherein, the conditions of the oxidation reaction are as follows: the relative humidity is 0-50%, and 0 is not included; the time is 0.5-15 days, the temperature of the oxidation reaction is 10-90 ℃, and the volume fraction of oxygen is 5-100%;
(3) And (3) placing the phosphorus-based negative electrode with the surface containing the oxide layer obtained in the step (2) into an electrolyte organic matter for in-situ carbonization reaction to obtain the phosphorus-based composite electrode.
Preferably, the preparation method of the phosphorus core material comprises the following steps: ball milling is carried out on the phosphorus simple substance; wherein the rotation speed of the ball milling treatment is 200-1000 rpm, preferably 250-600 rpm; and/or the ball milling treatment time is 8-24 hours.
Preferably, in step (3), the organic matter for an electrolyte is an electrolyte used in half-cell assembly.
Preferably, in the step (3), the half cell is assembled by adding an electrolyte organic material containing an electrolyte to the phosphorus-based negative electrode having the oxide layer on the surface obtained in the step (2) as a working electrode.
Preferably, in the step (3), the phosphorus-based negative electrode obtained in the step (2) and having an oxide layer on the surface thereof is used as a working electrode, a metal lithium sheet is used as an electrode, an electrolyte-containing organic material is added, and a separator is added to assemble the lithium ion half-cell.
Definition:
in the powder oxidation method, the oxidation degree is calculated according to the oxygen content, and the oxygen content refers to the mass percentage of oxygen atoms relative to the total mass of oxygen atoms and phosphorus atoms in the phosphorus core material with the surface containing the in-situ generated oxide layer. In the pole piece oxidation method, the oxidation degree is calculated according to oxygen content, wherein the oxygen content refers to mass percent of oxygen atoms in a phosphorus-based negative electrode with an in-situ generated oxide layer on the surface relative to the total mass of oxygen atoms, phosphorus atoms and carbon atoms; the carbon atom refers to a carbon atom in the carbon material as a conductive agent contained in the phosphorus-based anode before in-situ carbonization.
Degree of carbonization: the mass percentage of the carbon element (carbon element whose organic matter is carbonized by the oxide layer) in the original phosphorus powder. In the powder oxidation method, the carbon element includes only an organic substance for a binder and/or an organic substance for a dispersion liquid, which is carbonized by an oxide layer. In the pole piece oxidation method, the carbon element only comprises the carbon element carbonized by the oxide layer by the organic matters for the electrolyte.
Organic matter for binder: organic materials used as binders in the preparation of the electrode include, but are not limited to, polyvinylidene fluoride, styrene-butadiene rubber, polytetrafluoroethylene, butyl rubber, epoxy resin, polyacrylic acid, polyacrylonitrile, polyimide, and polyethyleneimine.
Organic matter for dispersion: in preparing the electrode, the organic matter used as the dispersion liquid includes, but is not limited to, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, N-methylpyrrole, dimethylsulfoxide, acetone, tetrahydrofuran, dimethylether, ethanol, and acetonitrile.
Organic matter for electrolyte: organic materials used as electrolytes in the assembly of the battery include, but are not limited to, ethylene carbonate, diethyl carbonate, polycarbonate, dimethyl carbonate, methylethyl carbonate, propylene carbonate, ethyl chlorocarbonate, ethyl propionate, propyl propionate, ethylene glycol dimethyl ether, 1, 3-dioxolane, diglyme, sulfolane, dimethyl sulfoxide, succinonitrile, and/or adiponitrile.
Powder oxidation method: placing the ball-milled phosphorus core material in an atmosphere containing oxygen for a certain time to obtain the phosphorus anode material containing the surface oxide layer. Wherein, the volume percentage V of oxygen in the atmosphere containing oxygen is: v is more than or equal to 5% and less than or equal to 100%, humidity RH is more than or equal to 0< RH and less than or equal to 50%, and oxidation time is controlled within 15 days.
Pole piece oxidation method: dispersing the ball-milled phosphor core material, the conductive agent and the binder in a dispersion liquid to obtain electrode slurry, coating the electrode slurry on the surface of a metal foil, drying to obtain a negative electrode plate, and placing the negative electrode plate in an atmosphere containing oxygen with certain humidity for a certain time to obtain the phosphor negative electrode plate with an oxide layer on the surface. Wherein, the volume percentage V of oxygen in the atmosphere containing oxygen is: v is more than or equal to 5% and less than or equal to 100%, humidity RH is more than or equal to 0< RH and less than or equal to 50%, and oxidation time is controlled within 15 days.
Taking powder oxidation as an example, the oxide layer (P x O y The mechanism of forming a carbonized layer on the surface of 0< x.ltoreq.2 and 0< y.ltoreq.5) is explained as follows: the cathode material with the surface containing phosphorus oxide is obtained after the phosphorus core material is naturally oxidized, the phosphorus oxide generated in situ on the surface of the phosphorus core material can be used as a dehydrating agent, and the cathode material can be subjected to bimolecular elimination reaction with organic matters (organic matters for adhesives and/or organic matters for dispersion liquid) containing hydrogen, oxygen or hydrogen and fluorine to remove H in organic matter molecules 2 O or HF generates conjugated double bond structure, and then forms carbonized layer on the surface of the oxide layer. Similarly, in the pole piece oxidation method, the phosphorus-based negative electrode containing the oxide layer and the organic matter (organic matter for electrolyte) of hydrogen oxygen or hydrogen fluorine undergo a bimolecular elimination reaction to remove H in the organic matter molecule 2 O or HF, to generate conjugated double bond structure, and further form carbonization layer on the surface of the phosphorus-based negative electrode containing oxidation layer, but because the phosphorus composite electrode sheet prepared by the electrode sheet oxidation method contains conductive agent carbon material, the content of carbon generated in carbonized organic matters is less than that of conductive agent carbon material, and the content of carbon obtained by partially carbonizing organic matters cannot be accurately measured by adopting the existing elemental analyzer, namely the numerical range of carbonization degree cannot be accurately measured.
The carbonization degree is mainly determined by the oxidation degree and the relative humidity in the natural oxidation degree, the oxidation degree and the relative humidity are main influencing factors of the carbonization degree, and the selected carbonized organic matters have a certain influence on the carbonization degree. The invention regulates and controls the oxidation degree, the relative humidity numerical range and the carbonized organic matters, thereby regulating and controlling the carbonization degree, and realizing the improvement of the multiplying power performance and the cycle performance of the battery.
To investigate the organic matter between the oxide layer and the organic matter for the dispersion and the organic matter for the binderInteraction was confirmed by the following characterization experimental data: taking N-methylpyrrolidone (NMP) as an example, the interaction between phosphorus oxide and organic substances for dispersion is illustrated: FIG. 1 shows NMP, P 2 O 5 NMP and P 2 O 5 Ultraviolet-visible absorption spectrum of the reaction product. Detection of NMP and P 2 O 5 Corresponding to the carbonization reaction occurring in the simulation example, P 2 O 5 Powder (main component of surface oxide layer of phosphorus core material is P 2 O 5 ) Added to NMP. NMP and NMP+P were reacted for 5h 2 O 5 Respectively evaporating samples of the sample (B) to dryness, and adding deionized water with the same amount to perform ultraviolet-visible absorption spectrum test; to remove residual P 2 O 5 Will P 2 O 5 The powder was dissolved by adding it to 10mL of deionized water with stirring, and the solution was also subjected to UV-visible absorption spectroscopy, the results of which are shown in FIG. 1. Deionized water is used as a back solution, and after the NMP sample is evaporated to dryness and P is evaporated to dryness 2 O 5 The solution after being dissolved in water has no absorption peak in the range of 200-800 nm, and NMP+P 2 O 5 Two absorption peaks appear at 220nm and 307nm, corresponding to pi-pi energy level transitions of electrons in c=c and n-pi energy level transitions of electrons in c=o, respectively, and the generation of c=c bonds demonstrates P 2 O 5 The powder and NMP interact, and the phosphorus material with the surface containing an oxide layer after natural oxidation can be proved to carbonize organic matters to form a carbonized layer.
Taking PVDF (NMP) as an example, the interaction between phosphorus oxide and organics for binder and organics for dispersion is described: FIG. 2 is a STEM (b) and corresponding line scan of (a) BP-5 product in PVDF (NMP). Firstly, oxidizing Black Phosphorus (BP) powder for 5 days (BP-5) under the condition of room temperature, putting a BP-5 sample in a vacuum drying oven, heating for 2 days, and fully removing water. The dried BP-5 was then added to an NMP solution of 3% PVDF by mass, stirred for 24 hours, the reacted powder was filtered and washed 3 times with cyclohexane to remove the effect of the remaining NMP liquid. The washed powder was dried in vacuo at 80℃for 24h. By conducting STEM line scanning on the reaction product of BP-5 and NMP solution (figure 2) containing PVDF, carbon element (carbon element carbonized by oxide layer) and nitrogen element are found in particles besides phosphorus element and oxygen element, which shows that carbonization reaction between the oxide layer generated in situ on the surface of black phosphorus and binder is indeed generated, and the reaction can strengthen the action between the black phosphorus and binder, thereby being beneficial to reducing interface resistance and improving the cycle stability of the phosphorus cathode.
In order to better understand the technical scheme of the present invention, the following describes the technical scheme of the present invention in detail with reference to specific embodiments.
The reagents/instrument sources used in the following examples and comparative examples are shown in table 1.
TABLE 1 information on reagents/instruments used in examples and comparative examples of the present invention
/>
Wherein, the oxidation degree test steps in the invention are as follows: weighing 50mg of the composite material after being placed for a period of time in an atmosphere containing oxygen, wrapping the composite material into a square shape by using tinfoil, testing the composite material by using an organic element analyzer, and obtaining the oxygen element with the mass percentage of oxidation degree from the testing result.
The carbonization degree test method comprises the following steps: 50mg of composite material carbonized by the binder and the dispersing agent is weighed, the composite material is wrapped into a square shape by tinfoil, and is tested by an organic element analyzer, and the carbonization degree can be calculated from the mass percent of carbon element obtained from the test result, wherein the concrete calculation formula is as follows:
wherein the mass of the raw phosphorus powder is 50mg of the mass of the raw phosphorus powder corresponding to the phosphorus-based anode material containing the oxide layer and the carbonized layer.
Example 1
Firstly, preparing a phosphorus-based anode material containing an in-situ generated oxide layer and a carbonized layer
Weighing red phosphorus, placing the red phosphorus in a zirconia ball milling tank, adding 4 large balls with the diameter of 10mm, 7 middle balls with the diameter of 5mm and 30 small balls with the diameter of 1mm into the tank, packaging in an argon glove box, placing in a ball mill, and performing mechanical ball milling treatment for 24 hours; wherein the rotation speed of the ball mill is 400rpm. The particle size of the phosphorus simple substance after ball milling is 300-500 nm.
And placing the phosphorus simple substance after ball milling treatment in air, and placing for 3 days to perform in-situ oxidation, wherein the humidity RH is controlled to be 10%, and the temperature is 25 ℃. And then, drying the phosphorus composite material after in-situ oxidation in a vacuum oven for 12 hours to remove trace water on the surface of the material, thereby obtaining the phosphorus composite material containing the in-situ oxidation layer.
Dispersing a binder (polyvinylidene fluoride, PVDF) in an N-methyl pyrrolidone (NMP) dispersion liquid, wherein the mass percentage of the binder is 1%; and then adding 100mg of the phosphorus composite material containing the oxide layer and the conductive agent (carbon black), wherein the mass ratio of the phosphorus composite material containing the oxide layer, the conductive agent (carbon black) and the binder (PVDF) is 8:1:1, magnetically stirring for 24 hours, and controlling the temperature T at 25 ℃. The oxidation layer on the surface of the phosphorus inner core in the process can carbonize a binder (PVDF) and a dispersion liquid (NMP), so as to generate a layer of organic carbonization layer, and the phosphorus-based anode material containing an in-situ oxidation layer and an in-situ carbonization layer is obtained, wherein the oxidation degree is 35%, and the carbonization degree is 30%.
(II) preparation of phosphorus-based composite electrode
And uniformly coating the electrode slurry which is uniformly mixed on the surface of a copper foil through an automatic coating machine, vacuum-drying for 12 hours at 70 ℃ to obtain a phosphorus-based composite electrode with a surface oxide layer and a carbonization layer, and cutting the phosphorus-based composite electrode into a 12mm round electrode plate for testing a lithium ion half battery.
(III) Assembly and testing of lithium ion batteries
In a glove box filled with argon, the above-mentioned tool is placed in a vacuum containerThe phosphorus-based composite electrode with a surface oxide layer and a carbonization layer is assembled with a metal lithium sheet to form a button cell, the specification of the button cell is CR2032 type, and the electrolyte is 1M LiPF 6 The membrane is a polypropylene membrane.
The lithium ion half-cell is subjected to constant-current charge and discharge test, the test system is a Wuhan blue electric cell test system, the test environment temperature is 28 ℃, and the cell is subjected to small-current activation (0.025 A.g) -1 (3 turns)), the test current density of the lithium ion half cell is 0.26 A.g -1 。
Fig. 3 is a scanning electron microscope picture of the phosphorus-based anode material containing only the surface oxide layer prepared in example 1, and the magnification is 8 ten thousand times, and it is seen that the phosphorus-based anode material containing only the surface oxide layer shows a spherical morphology.
FIG. 4 shows that the phosphorus-based anode material prepared in example 1 was assembled to a lithium ion half cell at 0.1 mV.s -1 Cyclic voltammogram at sweep rate.
Example 2
Firstly, preparing a phosphorus-based anode material containing an in-situ generated oxide layer and a carbonized layer
Weighing red phosphorus simple substance, placing the red phosphorus simple substance in a zirconia ball milling tank, adding 4 large balls with the diameter of 10mm, 7 middle balls with the diameter of 5mm and 30 small balls with the diameter of 1mm into the tank, packaging in an argon glove box, placing in a ball mill, and carrying out mechanical ball milling treatment for 999min; wherein the rotation speed of the ball mill is 350rpm. The particle size of the phosphorus simple substance after ball milling is in the range of 700 nm-800 nm.
And placing the phosphorus simple substance after ball milling treatment in air for 15 days for in-situ oxidation, controlling the humidity RH to be 5%, and controlling the temperature T to be 25 ℃. And then, drying the phosphorus composite material after in-situ oxidation in a vacuum oven for 12 hours to remove trace water on the surface of the in-situ oxidized phosphorus composite material, thereby obtaining the phosphorus composite material containing the in-situ oxidation layer.
Dispersing a binder (styrene butadiene rubber, SBR) in an ethanol dispersion liquid, wherein the mass percentage of the binder is 15%; then 100mg of the phosphorus composite material with an oxide layer and a conductive agent (super P) are added, wherein the mass ratio of the phosphorus composite material with the oxide layer, the conductive agent (super P) and a binder (SBR) is 7:1.5:1.5, the magnetic stirring is carried out for 12 hours, and the reaction temperature is controlled at 80 ℃. The oxidation layer on the surface of the phosphorus inner core in the process can be carbonized with a binder (SBR) and dispersion ethanol to generate an organic carbonization layer, so that the phosphorus-based anode material containing the in-situ oxidation layer and the in-situ carbonization layer is obtained, the oxidation degree is 50%, and the carbonization degree is 46%.
(II) preparation of phosphorus-based composite electrode
And uniformly coating the electrode slurry which is uniformly mixed on the surface of a copper foil through an automatic coating machine, vacuum-drying for 12 hours at 70 ℃ to obtain a phosphorus-based composite electrode with a surface oxide layer and a carbonization layer, and cutting the phosphorus-based composite electrode into a 12mm round electrode plate for testing a sodium ion half battery.
Assembly and testing of sodium ion batteries
In a glove box filled with argon, the phosphorus-based composite electrode with a surface oxide layer and a carbonization layer and a metal sodium sheet are assembled into a button cell, the specification of the button cell is CR2032 type, and the electrolyte is 1M NaPF 6 The membrane is a poly glass fiber membrane.
The sodium ion half-cell is subjected to constant-current charge and discharge test, the test system is a Wuhan blue electric cell test system, the test environment temperature is 28 ℃, and the cell is subjected to small-current activation (0.025 A.g) -1 (3 turns)), the test current density of the sodium-ion half cell is 0.26 A.g -1 。
Example 3
Firstly, preparing a phosphorus-based anode material containing an in-situ generated oxide layer and a carbonized layer
Weighing black phosphorus simple substance, placing the black phosphorus simple substance in a zirconia ball milling tank, adding 7 middle balls with the diameter of 5mm and 30 small balls with the diameter of 1mm of zirconia material into the tank, packaging in an argon glove box, placing the packaged black phosphorus simple substance in a ball mill, and performing mechanical ball milling treatment for 20 hours; wherein the rotation speed of the ball mill is 300rpm. The particle size of the phosphorus simple substance after ball milling is in the range of 1-10 mu m.
Placing the phosphorus simple substance after ball milling treatment in air for 1 day for in-situ oxidation, controlling humidity RH at 30%, and controlling temperature T at 25 ℃. And then, drying the in-situ oxidized phosphorus anode material in a vacuum oven for 12 hours to remove trace water on the surface of the in-situ oxidized phosphorus composite material, thereby obtaining the phosphorus composite material containing the in-situ oxidized layer.
Dispersing a binder (polyacrylic acid, PAA) in a dimethyl sulfoxide (DMSO) dispersion liquid, wherein the mass percentage of the binder is 7%; then 100mg of the phosphorus composite material with an oxide layer and a conductive agent (ketjen black) are added, wherein the mass ratio of the phosphorus composite material with an oxide layer, the conductive agent (ketjen black) and a binder (PAA) is 7:2:1, and the mixture is magnetically stirred for 6 hours, and the reaction temperature is 55 ℃. The oxidation layer on the surface of the phosphorus inner core can carbonize a binder (PAA) and a dispersion liquid (DMSO) to generate a layer of organic carbonization layer, so as to obtain the phosphorus-based anode material containing the in-situ oxidation layer and the in-situ carbonization layer, wherein the oxidation degree is 23%, and the carbonization degree is 20%.
(II) preparation of phosphorus-based composite electrode
And uniformly coating the electrode slurry which is uniformly mixed on the surface of a copper foil through an automatic coating machine, vacuum-drying for 12 hours at 70 ℃ to obtain a phosphorus composite electrode with a surface oxide layer and a carbonization layer, and cutting the phosphorus composite electrode into a 12mm round electrode plate for testing a potassium ion half battery.
Assembly and testing of (tri) potassium ion batteries
In a glove box filled with argon, assembling the phosphorus composite electrode with a surface oxide layer and a carbonization layer and a metal potassium sheet into a button cell, wherein the button cell has a CR2032 type specification, and the electrolyte is 1M KPF 6 The EC/DEC electrolyte of (C) was used as the separator.
The potassium ion half-cell is subjected to constant-current charge and discharge test, the test system is a Wuhan blue electric cell test system, the test environment temperature is 28 ℃, and the cell is subjected to small-current activation (0.025 A.g) -1 (3 turns)), the test current density of the lithium ion half cell is 0.26 A.g -1 。
Example 4
Firstly, preparing a phosphorus-based anode material containing an in-situ generated oxide layer and a carbonized layer
Weighing fiber phosphorus simple substances, placing the fiber phosphorus simple substances in a zirconia ball milling tank, adding 10 large balls with the diameter of 10mm, 15 middle balls with the diameter of 5mm and 40 small balls with the diameter of 1mm into the tank, packaging in an argon glove box, placing in a ball mill, and performing mechanical ball milling treatment for 12 hours; wherein the rotation speed of the ball mill is 500rpm. The particle size of the phosphorus simple substance after ball milling is in the range of 200-300 nm.
And placing the phosphorus simple substance subjected to ball milling treatment in air for 7 days for in-situ oxidation, controlling the humidity RH at 18%, and controlling the temperature T at 25 ℃. And then, drying the phosphorus composite material after in-situ oxidation in a vacuum oven for 12 hours to remove trace water on the surface of the in-situ oxidized phosphorus composite material, thereby obtaining the phosphorus composite material containing the in-situ oxidation layer.
Dispersing a binder (epoxy resin, ER) in a dimethyl sulfoxide (DMSO) dispersion liquid, wherein the mass percentage of the binder is 3%; then 100mg of the phosphorus composite material with the oxide layer and the conductive agent (carbon nano tube) are added, wherein the mass ratio of the phosphorus composite material with the oxide layer, the conductive agent (carbon nano tube) and the binder (ER) is 7:1:2, and the mixture is magnetically stirred for 3 hours at the temperature of 30 ℃. The oxidation layer on the surface of the phosphorus inner core can carbonize the binder (ER) and the dispersion liquid (DMSO) to generate a layer of organic carbonization layer, so as to obtain the phosphorus-based anode material containing the in-situ oxidation layer and the in-situ carbonization layer, wherein the oxidation degree is 44%, and the carbonization degree is 39%.
(II) preparation of phosphorus-based composite electrode
And uniformly coating the uniformly mixed electrode slurry on the surface of a copper foil through an automatic coating machine, vacuum drying at 70 ℃ for 12 hours to obtain a phosphorus composite electrode with a surface oxide layer and a carbonization layer, and cutting the phosphorus composite electrode into a 12mm round electrode plate for testing a lithium ion half battery.
(III) Assembly and testing of lithium ion batteries
The assembly and testing of the lithium ion half-cell was the same as in example 1.
Example 5
Firstly, preparing a phosphorus-based anode material containing an in-situ generated oxide layer and a carbonized layer
Weighing red phosphorus simple substance, placing the red phosphorus simple substance in a zirconia ball milling tank, adding 4 large balls with the zirconia material diameter of 10mm into the tank, packaging in an argon glove box, placing the packaged red phosphorus simple substance in a ball mill, and performing mechanical ball milling treatment for 15 hours; wherein the rotation speed of the ball mill is 250rpm. The particle size of the phosphorus simple substance after ball milling is in the range of 45-50 mu m.
And placing the phosphorus simple substance subjected to ball milling treatment in air for 0.5 days for in-situ oxidation, controlling the humidity RH to be 20%, and controlling the temperature T to be 25 ℃. And then, drying the phosphorus composite material after in-situ oxidation in a vacuum oven for 12 hours to remove trace water on the surface of the in-situ oxidized phosphorus composite material, thereby obtaining the phosphorus composite material containing the in-situ oxidation layer.
Dispersing a binder (polyvinylidene fluoride, PVDF) in an N-methyl pyrrolidone (NMP) dispersion liquid, wherein the mass percentage of the binder is 3%; then 100mg of the phosphorus composite material with an oxide layer and a conductive agent (carbon black) are added, wherein the mass ratio of the phosphorus composite material with the oxide layer, the conductive agent (carbon black) and a binder (PVDF) is 6:2:2, and the mixture is magnetically stirred for 9 hours, and the reaction temperature is 25 ℃. The oxidation layer on the surface of the phosphorus inner core in the process can carbonize a binder (PVDF) and a dispersion liquid (NMP), so as to generate a layer of organic carbonization layer, and the phosphorus-based anode material containing the in-situ oxidation layer and the in-situ carbonization layer is obtained, wherein the oxidation degree is 20%, and the carbonization degree is 16%.
(II) preparation of phosphorus-based composite electrode
And uniformly coating the uniformly mixed electrode slurry on the surface of a copper foil through an automatic coating machine, vacuum drying at 70 ℃ for 12 hours to obtain a phosphorus composite electrode with a surface oxide layer and a carbonization layer, and cutting the phosphorus composite electrode into a 12mm round electrode plate for testing a lithium ion half battery.
(III) Assembly and testing of lithium ion batteries
The assembly and testing of the lithium ion half-cell was the same as in example 1.
Example 6
Weighing black phosphorus simple substance, placing the black phosphorus simple substance in a zirconia ball milling tank, adding 10 large balls with the diameter of 10mm, 15 middle balls with the diameter of 5mm and 40 small balls with the diameter of 1mm into the tank, packaging in an argon glove box, placing in a ball mill, and performing mechanical ball milling treatment for 8 hours; wherein the rotation speed of the ball mill is 350rpm. The particle size of the phosphorus simple substance after ball milling is 300-500 nm.
And placing the phosphorus simple substance subjected to ball milling in air for 2 days for in-situ oxidation, controlling the humidity RH at 40%, and controlling the temperature T at 25 ℃. And drying the in-situ oxidized phosphorus composite material in a vacuum oven for 12 hours to remove trace water on the surface of the in-situ oxidized phosphorus composite material, thereby obtaining the phosphorus composite material containing the in-situ oxidized layer.
Dispersing a binder (styrene-butadiene rubber, SBR) in an ethanol (EtOH) dispersion liquid, wherein the mass percentage of the binder is 5%; then 100mg of the phosphorus composite material with an oxide layer and a conductive agent (carbon black) are added, wherein the mass ratio of the phosphorus composite material with the oxide layer, the conductive agent (carbon black) and a binder (SBR) is 95:2.5:2.5, and the mixture is magnetically stirred for 12 hours, and the reaction temperature is 50 ℃. The oxidation layer on the surface of the phosphorus inner core can be carbonized with a binder (SBR) and a dispersion liquid (EtOH) to generate a layer of organic carbonized layer, and the phosphorus-based anode material containing an in-situ oxidation layer and an in-situ carbonized layer is obtained, wherein the oxidation degree is 29%, and the carbonization degree is 24%.
(II) preparation of phosphorus-based composite electrode
And uniformly coating the uniformly mixed electrode slurry on the surface of a copper foil through an automatic coating machine, vacuum drying at 70 ℃ for 12 hours to obtain a phosphorus composite electrode with a surface oxide layer and a carbonization layer, and cutting the phosphorus composite electrode into a 12mm round electrode plate for testing a lithium ion half battery.
(III) Assembly and testing of lithium ion batteries
The assembly and testing of the lithium ion half-cell was the same as in example 1.
Example 7
Firstly, preparing a phosphorus-based anode material containing an in-situ generated oxide layer and a carbonized layer
Weighing black phosphorus simple substance, placing the black phosphorus simple substance in a zirconia ball milling tank, adding 10 balls with the diameter of 10mm, 15 balls with the diameter of 5mm and 40 balls with the diameter of 1mm into the tank, packaging in an argon glove box, placing in a ball mill, and performing mechanical ball milling treatment for 20 hours; wherein the rotation speed of the ball mill is 550rpm. The particle size of the phosphorus simple substance after ball milling is in the range of 100-300 nm.
Placing the phosphorus simple substance after ball milling treatment in air for 15 days for in-situ oxidation, controlling humidity RH at 15%, and controlling temperature T at 25 ℃. And then, drying the phosphorus composite material after in-situ oxidation in a vacuum oven for 12 hours to remove trace water on the surface of the in-situ oxidized phosphorus composite material, thereby obtaining the phosphorus composite material containing the in-situ oxidation layer.
Dispersing a binder (polyvinylidene fluoride, PVDF) in an N-methyl pyrrolidone (NMP) dispersion liquid, wherein the mass percentage of the binder is 4%; then 100mg of the phosphorus composite material with an oxide layer and a conductive agent (carbon black) are added, wherein the mass ratio of the phosphorus composite material with the oxide layer, the conductive agent (carbon black) and a binder (PVDF) is 8:1:1, and the mixture is magnetically stirred for 12 hours, and the reaction temperature is 60 ℃. The oxidation layer on the surface of the phosphorus inner core can be carbonized with a binder (PVDF) and N-methyl pyrrolidone dispersion liquid to generate a layer of organic carbonization layer, so that the phosphorus-based anode material containing the in-situ oxidation layer and the in-situ carbonization layer is obtained, the oxidation degree is 49%, and the carbonization degree is 45%.
(II) preparation of phosphorus-based composite electrode
And uniformly coating the uniformly mixed electrode slurry on the surface of a copper foil through an automatic coating machine, vacuum drying at 70 ℃ for 12 hours to obtain a phosphorus composite electrode with a surface oxide layer and a carbonization layer, and cutting the phosphorus composite electrode into a 12mm round electrode plate for testing a lithium ion half battery.
(III) Assembly and testing of lithium ion batteries
The assembly and testing of the lithium ion half-cell was the same as in example 1.
Example 8
First, lithium ion battery is prepared
Weighing red phosphorus simple substance, placing the red phosphorus simple substance in a zirconia ball milling tank, adding 10 large balls with the diameter of 1cm, 15 middle balls with the diameter of 0.5cm and 40 small balls with the diameter of 3mm into the tank, packaging in an argon glove box, placing in a ball mill, and performing mechanical ball milling treatment for 12 hours; wherein the rotation speed of the ball mill is 400rpm. The particle size of the phosphorus simple substance after ball milling is 300-500 nm.
Firstly, 100mg of freshly prepared ball-milled phosphorus anode material, a conductive agent (carbon black) and a binder (PVDF) are mixed according to a mass ratio of 8:1:1, N-methyl pyrrolidone (NMP) is used as a dispersion liquid, magnetic stirring is carried out for 12 hours at 30 ℃ to obtain uniformly mixed electrode slurry, the electrode slurry is uniformly coated on the surface of copper foil through an automatic coating machine, vacuum drying is carried out for 12 hours at 70 ℃, and the electrode slurry is cut into 12mm round electrode slices, so that a common phosphorus-based anode is obtained.
In order to obtain the phosphorus-based negative electrode plate with the in-situ oxidation layer, the material needs to be placed in air for 1 day to perform in-situ oxidation, the humidity RH is controlled to be 2%, and the temperature T is controlled to be 25 ℃. And then, drying the phosphorus-based negative electrode after in-situ oxidation in a vacuum oven for 12 hours to remove trace water on the surface of the in-situ oxidized phosphorus-based negative electrode, thereby obtaining the phosphorus-based negative electrode with the in-situ oxidation layer.
In a glove box filled with argon, the phosphorus-based negative electrode with the surface oxide layer is used as a working electrode, and a metal lithium sheet is used as a counter electrode, wherein 100 mu L of 1mol/L LiPF is added based on 1mg of the mass of the electrode material (i.e. the mass of the electrode sheet with the copper foil removed) 6 The ethylene carbonate/dimethyl carbonate (EC/DMC) electrolyte of (a) was normally assembled into a button cell having a CR2032 type specification using a polypropylene separator as a separator, and was allowed to stand at 25 ℃ for 12 hours. The standing process and the subsequent formation and circulation processes can carbonize the electrolyte to form the phosphorus-based anode with the surface oxide layer and the carbonized layer.
Testing of lithium ion batteries
The lithium ion half-cell is subjected to constant-current charge and discharge test, the test system is a Wuhan blue electric cell test system, the test environment temperature is 28 ℃, and the cell is subjected to small-current activation (0.025 A.g) -1 (3 turns)), the test current density of the lithium ion half cell is 0.26 A.g -1 。
Example 9
First, lithium ion battery is prepared
Weighing red phosphorus simple substance, placing the red phosphorus simple substance in a zirconia ball milling tank, adding 10 large balls with the diameter of 1cm, 15 middle balls with the diameter of 0.5cm and 40 small balls with the diameter of 3mm into the tank, packaging in an argon glove box, placing in a ball mill, and performing mechanical ball milling treatment for 12 hours; wherein the rotation speed of the ball mill is 400rpm. The particle size of the phosphorus simple substance after ball milling is 300-500 nm.
Firstly, 100mg of freshly prepared ball-milled phosphorus anode material, a conductive agent (acetylene black) and a binder (SBR) are mixed according to the mass ratio of 7:1.5:1.5, ethanol is used as a dispersion liquid, the temperature T is controlled at 30 ℃, the mixture is magnetically stirred for 6 hours to obtain uniformly mixed electrode slurry, the electrode slurry is uniformly coated on the surface of a copper foil through an automatic coating machine, vacuum drying is carried out for 12 hours at 70 ℃, and the electrode slurry is cut into 12mm round electrode slices, so that a common phosphorus-based anode is obtained.
In order to obtain the phosphorus-based negative electrode with the in-situ oxidation layer, the pole piece is placed in air for 3 days to carry out in-situ oxidation, the humidity RH is controlled to be 10%, and the temperature T is controlled to be 35 ℃. The phosphorus-based negative electrode after in-situ oxidation was dried in a vacuum oven for 12 hours to remove trace water from the surface of the phosphorus-based negative electrode after in-situ oxidation. The electrode is a phosphorus-based negative electrode with an in-situ oxide layer.
In a glove box filled with argon, the above phosphorus-based negative electrode with a surface oxide layer was used as a working electrode, a metal lithium sheet was used as a counter electrode, wherein based on the mass of the electrode material, 2mg was added to 50 μl of 1mol/L dioxolane/ethylene glycol dimethyl ether (DOL/DME) electrolyte of LiPF6, and a polypropylene separator was used as a separator, and the battery was normally assembled into a button cell having a CR2032 type cell size and allowed to stand at room temperature for 12 hours. The standing process and the subsequent formation and circulation processes can carbonize the electrolyte to form the phosphorus-based anode with the surface oxide layer and the carbonized layer.
Testing of lithium ion batteries
The lithium ion half-cell is subjected to constant-current charge and discharge test, the test system is a Wuhan blue electric cell test system, the test environment temperature is 28 ℃, and the cell is subjected to small-current activation (0.025 A.g) -1 (3 turns)), the test current density of the lithium ion half cell is 0.26 A.g -1 。
Example 10
First, lithium ion battery is prepared
Weighing red phosphorus simple substance, placing the red phosphorus simple substance in a zirconia ball milling tank, adding 10 large balls with the diameter of 1cm, 15 middle balls with the diameter of 0.5cm and 40 small balls with the diameter of 3mm into the tank, packaging in an argon glove box, placing in a ball mill, and performing mechanical ball milling treatment for 12 hours; wherein the rotation speed of the ball mill is 400rpm. The particle size of the phosphorus simple substance after ball milling is 300-500 nm.
Firstly, 100mg of freshly prepared ball-milled phosphorus anode material, a conductive agent (super P) and a binder (PAA) are mixed according to a mass ratio of 7:2:1, N-methyl pyrrolidone is used as a dispersion liquid, magnetic stirring is carried out for 3 hours at 35 ℃ to obtain uniformly mixed electrode slurry, the electrode slurry is uniformly coated on the surface of copper foil through an automatic coating machine, vacuum drying is carried out for 12 hours at 70 ℃, and the electrode slurry is cut into 12mm round electrode slices, so that a common phosphorus-based anode is obtained.
In order to obtain the phosphorus-based negative electrode with the in-situ oxidation layer, the pole piece is placed in air for 2 days to carry out in-situ oxidation, the humidity RH is controlled to be 30%, and the temperature T is controlled to be 35 ℃. The phosphorus-based negative electrode after in-situ oxidation was dried in a vacuum oven for 12 hours to remove trace water from the surface of the phosphorus-based negative electrode after in-situ oxidation. The electrode is a phosphorus-based negative electrode with an in-situ oxide layer.
In a glove box filled with argon, the above phosphorus-based anode with surface oxide layer was used as a working electrode, and a metallic lithium sheet was used as a counter electrode, wherein 1mol/L LiPF of 50. Mu.L was added based on 1.5mg of the mass of the electrode material 6 Sulfolane/dimethyl sulfoxide (SL/DMSO) electrolyte, using polypropylene diaphragm as diaphragm, is normally assembled into button cell, the specification of button cell is CR2032 type, and is left stand for 12h. The standing process and the subsequent formation and circulation processes can carbonize the electrolyte to form the phosphorus-based anode with the surface oxide layer and the carbonized layer.
Testing of lithium ion batteries
The lithium ion half-cell is subjected to constant-current charge and discharge test, the test system is a Wuhan blue electric cell test system, the test environment temperature is 28 ℃, and the cell is subjected to small-current activation (0.025 A.g) -1 (3 turns)), the test current density of the lithium ion half cell is 0.26 A.g -1 。
Example 11
First, lithium ion battery is prepared
Weighing red phosphorus simple substance, placing the red phosphorus simple substance in a zirconia ball milling tank, adding 10 large balls with the diameter of 1cm, 15 middle balls with the diameter of 0.5cm and 40 small balls with the diameter of 3mm into the tank, packaging in an argon glove box, placing in a ball mill, and performing mechanical ball milling treatment for 12 hours; wherein the rotation speed of the ball mill is 400rpm. The particle size of the phosphorus simple substance after ball milling is 300-500 nm.
Firstly, 100mg of freshly prepared ball-milled phosphorus anode material, a conductive agent (carbon black) and a binder (styrene-butadiene rubber, SBR) are mixed according to a mass ratio of 7:1.5:1.5, ethanol is used as a dispersion, the temperature T is controlled at 30 ℃, magnetic stirring is carried out for 6 hours to obtain uniformly mixed electrode slurry, the electrode slurry is uniformly coated on the surface of a copper foil through an automatic coating machine, vacuum drying is carried out for 12 hours at 70 ℃, and the electrode slurry is cut into 12mm round electrode slices, so that a common phosphorus-based anode is obtained.
In order to obtain the phosphorus-based negative electrode with the in-situ oxidation layer, the pole piece is placed in air for 15 days to carry out in-situ oxidation, the humidity RH is controlled to be 10%, and the temperature T is controlled to be 35 ℃. The phosphorus-based negative electrode after in-situ oxidation was dried in a vacuum oven for 12 hours to remove trace water from the surface of the phosphorus-based negative electrode after in-situ oxidation. The electrode is a phosphorus-based negative electrode with an in-situ oxide layer.
In a glove box filled with argon, the above phosphorus-based anode with surface oxide layer was used as a working electrode, and a metallic lithium sheet was used as a counter electrode, wherein 50. Mu.L of 1mol/L LiPF was added based on 2mg of the mass of the electrode material 6 The dioxolane/ethylene glycol dimethyl ether (DOL/DME) electrolyte is normally assembled into a button cell by using a polypropylene diaphragm as a diaphragm, the specification of the button cell is CR2032 type, and the button cell is left to stand for 12 hours at room temperature. The standing process and the subsequent formation and circulation processes can carbonize the electrolyte to form the phosphorus-based anode with the surface oxide layer and the carbonized layer.
Testing of lithium ion batteries
The lithium ion half-cell is subjected to constant-current charge and discharge test, the test system is a Wuhan blue electric cell test system, the test environment temperature is 28 ℃, and the cell is subjected to small-current activation (0.025 A.g) -1 (3Circle)), the test current density of the lithium ion half cell is 0.26 A.g -1 。
Example 12
First, lithium ion battery is prepared
Weighing red phosphorus simple substance, placing the red phosphorus simple substance in a zirconia ball milling tank, adding 10 large balls with the diameter of 1cm, 15 middle balls with the diameter of 0.5cm and 40 small balls with the diameter of 3mm into the tank, packaging in an argon glove box, placing in a ball mill, and performing mechanical ball milling treatment for 12 hours; wherein the rotation speed of the ball mill is 400rpm. The particle size of the phosphorus simple substance after ball milling is 300-500 nm.
Firstly, 100mg of freshly prepared ball-milled phosphorus anode material, a conductive agent (carbon black) and a binder (SBR) are mixed according to the mass ratio of 7:1.5:1.5, ethanol is used as a dispersion liquid, the temperature T is controlled at 30 ℃, magnetic stirring is carried out for 6 hours to obtain uniformly mixed electrode slurry, the electrode slurry is uniformly coated on the surface of a copper foil through an automatic coating machine, vacuum drying is carried out for 12 hours at 70 ℃, and the electrode slurry is cut into 12mm round electrode slices, so that a common phosphorus-based anode is obtained.
In order to obtain the phosphorus-based negative electrode with the in-situ oxidation layer, the pole piece is placed in air for 15 days to carry out in-situ oxidation, the humidity RH is controlled to be 45%, and the temperature T is controlled to be 35 ℃. The phosphorus-based negative electrode after in-situ oxidation was dried in a vacuum oven for 12 hours to remove trace water from the surface of the phosphorus-based negative electrode after in-situ oxidation. The electrode is a phosphorus-based negative electrode with an in-situ oxide layer.
In a glove box filled with argon, the above phosphorus-based anode with surface oxide layer was used as a working electrode, and a metallic lithium sheet was used as a counter electrode, wherein 50. Mu.L of 1mol/L LiPF was added based on 2mg of the mass of the electrode material 6 The dioxolane/ethylene glycol dimethyl ether (DOL/DME) electrolyte is normally assembled into a button cell by using a polypropylene diaphragm as a diaphragm, the specification of the button cell is CR2032 type, and the button cell is left to stand for 12 hours at room temperature. The standing process and the subsequent formation and circulation processes can carbonize the electrolyte to form the phosphorus-based anode with the surface oxide layer and the carbonized layer.
Testing of lithium ion batteries
The lithium ion half-cell is subjected to constant-current charge and discharge test, the test system is a Wuhan blue electric cell test system, the test environment temperature is 28 ℃, and the cell is subjected to small-current activation (0.025 A.g) -1 (3 turns)), the test current density of the lithium ion half cell is 0.26 A.g -1 。
Comparative example 1
The difference from example 1 is that: the phosphorus-based negative electrode material of example 1 did not contain an oxide layer or a carbide layer. Dispersing a binder (polyvinylidene fluoride, PVDF) in an N-methyl pyrrolidone (NMP) dispersion liquid, wherein the mass percentage of the binder is 1%; 100mg of freshly prepared ball-milled phosphorus simple substance, a conductive agent (carbon black) and a binder (PVDF) are mixed according to a mass ratio of 8:1:1, N-methylpyrrolidone (NMP) is used as a dispersion liquid, magnetic stirring is carried out for 24 hours, and the temperature T is controlled at 25 ℃ to obtain the uniformly mixed electrode slurry.
And uniformly coating the electrode slurry which is uniformly mixed on the surface of a copper foil through an automatic coating machine, and vacuum drying at 70 ℃ for 12 hours to obtain the phosphorus-based composite electrode without a surface oxide layer and a carbonization layer, and cutting the phosphorus-based composite electrode into a 12mm round electrode plate for testing a lithium ion half battery.
The assembly and testing of the lithium ion half-cell was the same as in example 1.
Comparative example 2
The difference from example 2 is that: the phosphorus negative electrode material of example 2 did not contain an oxide layer or a carbonized layer. Dispersing a binder (styrene butadiene rubber, SBR) in an ethanol dispersion liquid, wherein the mass percentage of the binder is 15%; 100mg of freshly prepared ball-milled phosphorus simple substance is mixed with a conductive agent (super P) and a binder (SBR) according to the mass ratio of 7:1.5:1.5, ethanol is used as a dispersion liquid, magnetic stirring is carried out for 12 hours, and the temperature is controlled at 80 ℃ to obtain the uniformly mixed electrode slurry.
And uniformly coating the electrode slurry which is uniformly mixed on the surface of a copper foil through an automatic coating machine, and vacuum drying at 70 ℃ for 12 hours to obtain a base composite electrode which does not contain a surface oxide layer and a carbonization layer, and cutting the base composite electrode into a 12mm round electrode plate for testing a sodium ion half battery.
The assembly and testing of the sodium half-cell was the same as in example 2.
Comparative example 3
The difference from example 3 is that: the phosphorus-based negative electrode material of example 3 did not contain the surface oxide layer and the carbonized layer. Dispersing a binder (polyacrylic acid, PAA) in a dimethyl sulfoxide (DMSO) dispersion liquid, wherein the mass percentage of the binder is 7%; 100mg of freshly prepared ball-milled phosphorus simple substance, a conductive agent (ketjen black) and a binder (PAA) are mixed according to a mass ratio of 7:2:1, dimethyl sulfoxide (DMSO) is used as a dispersion liquid, and the mixture is magnetically stirred for 6 hours at a temperature of 55 ℃ to obtain uniformly mixed electrode slurry.
And uniformly coating the electrode slurry which is uniformly mixed on the surface of a copper foil through an automatic coating machine, and vacuum drying at 70 ℃ for 12 hours to obtain a phosphorus composite electrode which does not contain a surface oxide layer and a carbonization layer, and cutting the phosphorus composite electrode into a 12mm round electrode plate for testing a potassium ion half battery.
The assembly and testing of the potassium half cell was the same as in example 3.
Comparative example 4
The difference from example 4 is that: the phosphorus negative electrode material of example 4 did not contain a surface oxide layer or a carbonized layer. Dispersing a binder (epoxy resin, ER) in a dimethyl sulfoxide (DMSO) dispersion liquid, wherein the mass percentage of the binder is 3%; 100mg of freshly prepared ball-milled phosphorus simple substance, a conductive agent (carbon nano tube) and a binder (ER) are mixed according to a mass ratio of 7:1:2, dimethyl sulfoxide (DMSO) is used as a dispersion liquid, and the mixture is magnetically stirred for 3 hours at a temperature of 30 ℃ to obtain uniformly mixed electrode slurry.
And uniformly coating the electrode slurry which is uniformly mixed on the surface of a copper foil through an automatic coating machine, and vacuum drying at 70 ℃ for 12 hours to obtain a phosphorus composite electrode which does not contain a surface oxide layer and a carbonization layer, and cutting the phosphorus composite electrode into a 12mm round electrode plate for testing a lithium ion half battery.
The assembly and testing of the lithium ion half-cell was the same as in example 1.
Comparative example 5
The difference from example 5 is that: the phosphorus negative electrode material of example 5 did not contain a surface oxide layer or a carbonized layer. Dispersing a binder (polyvinylidene fluoride, PVDF) in an N-methyl pyrrolidone (NMP) dispersion liquid, wherein the mass percentage of the binder is 3%; 100mg of freshly prepared ball-milled phosphorus simple substance, a conductive agent (carbon black) and a binder (PVDF) are mixed according to a mass ratio of 6:2:2, N-methylpyrrolidone (NMP) is used as a dispersion liquid, and the mixture is magnetically stirred for 9 hours at a temperature of 25 ℃ to obtain electrode slurry which is uniformly mixed. And uniformly coating the electrode slurry which is uniformly mixed on the surface of a copper foil through an automatic coating machine, and vacuum drying at 70 ℃ for 12 hours to obtain a phosphorus composite electrode which does not contain a surface oxide layer and a carbonization layer, and cutting the phosphorus composite electrode into a 12mm round electrode plate for testing a lithium ion half battery.
The assembly and testing of the lithium ion half-cell was the same as in example 1.
Comparative example 6
The difference from example 6 is that: the phosphorus negative electrode material of example 6 did not contain a surface oxide layer or a carbonized layer. Dispersing a binder (styrene-butadiene rubber, SBR) in an ethanol (EtOH) dispersion liquid, wherein the mass percentage of the binder is 5%; 100mg of freshly prepared ball-milled phosphorus simple substance, a conductive agent (carbon black) and a binder (SBR) are mixed according to a mass ratio of 95:2.5:2.5, ethanol (EtOH) is taken as a dispersion liquid, and magnetic stirring is carried out for 12 hours, so that electrode slurry with uniform mixing is obtained.
And uniformly coating the electrode slurry which is uniformly mixed on the surface of a copper foil through an automatic coating machine, and vacuum drying at 70 ℃ for 12 hours to obtain a phosphorus composite electrode which does not contain a surface oxide layer and a carbonization layer, and cutting the phosphorus composite electrode into a 12mm round electrode plate for testing a lithium ion half battery.
The assembly and testing of the lithium ion half-cell was the same as in example 1.
Comparative example 7
The difference from example 7 is that: the phosphorus negative electrode material of example 7 did not contain a surface oxide layer or a carbonized layer. Dispersing a binder (polyvinylidene fluoride, PVDF) in an N-methyl pyrrolidone (NMP) dispersion liquid, wherein the mass percentage of the binder is 4%; 100mg of freshly prepared ball-milled phosphorus simple substance, a conductive agent (carbon black) and a binder (PVDF) are mixed according to a mass ratio of 8:1:1, acetone is used as a dispersion liquid, and magnetic stirring is carried out for 12 hours at a temperature of 60 ℃ to obtain uniformly mixed electrode slurry.
And uniformly coating the electrode slurry which is uniformly mixed on the surface of a copper foil through an automatic coating machine, and vacuum drying at 70 ℃ for 12 hours to obtain a phosphorus composite electrode which does not contain a surface oxide layer and a carbonization layer, and cutting the phosphorus composite electrode into a 12mm round electrode plate for testing a lithium ion half battery.
The assembly and testing of the lithium ion half-cell was the same as in example 1.
Comparative example 8
The humidity of air was 80% compared to example 3, and the rest of the experimental conditions were exactly the same as in example 3.
Weighing black phosphorus simple substance, placing the black phosphorus simple substance in a zirconia ball milling tank, adding 7 middle balls with the diameter of 5mm and 30 small balls with the diameter of 1mm of zirconia material into the tank, packaging in an argon glove box, placing the packaged black phosphorus simple substance in a ball mill, and performing mechanical ball milling treatment for 20 hours; wherein the rotation speed of the ball mill is 300rpm. The particle size of the phosphorus simple substance after ball milling is in the range of 1-10 mu m.
Placing the phosphorus simple substance after ball milling treatment in air for 1 day for in-situ oxidation, controlling humidity RH at 80%, and controlling temperature T at 25 ℃. And then, drying the in-situ oxidized phosphorus anode material in a vacuum oven for 12 hours to remove trace water on the surface of the in-situ oxidized phosphorus composite material, thereby obtaining the phosphorus composite material containing the in-situ oxidized layer.
Dispersing a binder (polyacrylic acid, PAA) in a dimethyl sulfoxide (DMSO) dispersion liquid, wherein the mass percentage of the binder is 7%; then 100mg of the phosphorus composite material with an oxide layer and a conductive agent (ketjen black) are added, wherein the mass ratio of the phosphorus composite material with an oxide layer, the conductive agent (ketjen black) and a binder (PAA) is 7:2:1, and the mixture is magnetically stirred for 6 hours, and the reaction temperature is 55 ℃. The oxidation layer on the surface of the phosphorus inner core can carbonize a binder (PAA) and a dispersion liquid (DMSO) to generate a layer of organic carbonization layer, so as to obtain the phosphorus-based anode material containing the in-situ oxidation layer and the in-situ carbonization layer, wherein the oxidation degree is 23%, and the carbonization degree is 2%.
And uniformly coating the electrode slurry which is uniformly mixed on the surface of a copper foil through an automatic coating machine, vacuum-drying for 12 hours at 70 ℃ to obtain a phosphorus composite electrode with a surface oxide layer and a carbonization layer, and cutting the phosphorus composite electrode into a 12mm round electrode plate for testing a potassium ion half battery.
In a glove box filled with argon, assembling the phosphorus composite electrode with a surface oxide layer and a carbonization layer and a metal potassium sheet into a button cell, wherein the button cell has a CR2032 type specification, and the electrolyte is 1M KPF 6 The EC/DEC electrolyte of (C) was used as the separator.
The potassium ion half-cell is subjected to constant-current charge and discharge test, the test system is a Wuhan blue electric cell test system, the test environment temperature is 28 ℃, and the cell is subjected to small-current activation (0.025 A.g) -1 (3 turns)), the test current density of the lithium ion half cell is 0.26 A.g -1 。
Comparative example 9
The difference from example 8 is that: the electrode was a phosphorus-based negative electrode containing no surface oxide layer or carbide layer in example 8. 100mg of freshly prepared ball-milled phosphorus simple substance, a conductive agent (carbon black) and a binder (PVDF) are mixed according to a mass ratio of 8:1:1, N-methylpyrrole (NMP) is taken as a dispersion liquid, magnetic stirring is carried out for 12 hours at 30 ℃ to obtain uniformly mixed electrode slurry, the electrode slurry is uniformly coated on the surface of a copper foil through an automatic coating machine, vacuum drying is carried out for 12 hours at 70 ℃, and the electrode slurry is cut into 12mm round electrode slices, so that a common phosphorus-based negative electrode is obtained. In a glove box filled with argon, the common phosphorus-based negative electrode is used as a working electrode, a metal lithium sheet is used as a counter electrode, wherein 100 mu L of 1mol/L LiPF is added based on 1mg of the mass of the electrode material 6 The ethylene carbonate/dimethyl carbonate (EC/DMC) electrolyte of (a) was normally assembled into a button cell, having a CR2032 type specification, using a polypropylene separator as the separator. The lithium ion half-cell is subjected to constant-current charge and discharge test, the test system is a Wuhan blue electric cell test system, the test environment temperature is 28 ℃, and the cell is subjected to small-current activation (0.025 A.g) -1 (3 turns)), the test current density of the lithium ion half cell is 0.26 A.g -1 。
Comparative example 10
The difference from example 9 is that: the phosphorus-based negative electrode of example 9 did not contain a surface oxide layer or a carbonized layer. First 100mg of freshMixing freshly prepared ball-milled phosphorus simple substance, a conductive agent (carbon black) and a binder (SBR) according to a mass ratio of 7:1.5:1.5, taking ethanol as a dispersion liquid, magnetically stirring at a temperature T of 30 ℃ for 6 hours to obtain uniformly mixed electrode slurry, uniformly coating the electrode slurry on the surface of a copper foil through an automatic coating machine, vacuum-drying at 70 ℃ for 12 hours, and cutting the electrode slurry into 12mm round electrode slices to obtain a common phosphorus-based negative electrode. In a glove box filled with argon, the above-mentioned ordinary phosphorus-based negative electrode was used as a working electrode, and a metallic lithium sheet was used as a counter electrode, wherein 50 μl of 1mol/L dioxolane/ethylene glycol dimethyl ether (DOL/DME) electrolyte of LiPF6 was added based on the mass of the electrode material, and a button cell was normally assembled using a polypropylene separator as a separator, the button cell having a size of CR2032 type. The lithium ion half-cell is subjected to constant-current charge and discharge test, the test system is a Wuhan blue electric cell test system, the test environment temperature is 28 ℃, and the cell is subjected to small-current activation (0.025 A.g) -1 (3 turns)), the test current density of the lithium ion half cell is 0.26 A.g -1 。
Comparative example 11
The difference from example 10 is that: the phosphorus-based negative electrode of example 10 did not contain a surface oxide layer or a carbonized layer. Firstly, 100mg of freshly prepared ball-milled phosphorus simple substance, a conductive agent (carbon black) and a binder (PAA) are mixed according to a mass ratio of 7:2:1, N-methyl pyrrolidone is used as a dispersion liquid, the temperature T is controlled at 35 ℃ and magnetically stirred for 3 hours to obtain uniformly mixed electrode slurry, the electrode slurry is uniformly coated on the surface of a copper foil through an automatic coating machine, vacuum drying is carried out for 12 hours at 70 ℃, and the electrode slurry is cut into 12mm round electrode slices, so that a common phosphorus-based negative electrode is obtained. In a glove box filled with argon, the above-mentioned ordinary phosphorus-based negative electrode was used as a working electrode, and a metallic lithium sheet was used as a counter electrode, wherein a sulfolane/dimethyl sulfoxide (SL/DMSO) electrolyte of 1mol/L LiPF6 was added in an amount of 50 μl based on the mass of the electrode material, and a button cell was normally assembled using a polypropylene separator as a separator, the button cell having a size of CR2032 type. The lithium ion half-cell is subjected to constant-current charge and discharge test, the test system is a Wuhan blue electric cell test system, the test environment temperature is 28 ℃, and the cell is subjected to small-current activation (0.0) 25A·g -1 (3 turns)), the test current density of the lithium ion half cell is 0.26 A.g -1 。
Comparative example 12
The humidity of air was 80% compared to example 8, and the rest of the experimental conditions were exactly the same as in example 8. Weighing red phosphorus simple substance, placing the red phosphorus simple substance in a zirconia ball milling tank, adding 10 large balls with the diameter of 1cm, 15 middle balls with the diameter of 0.5cm and 40 small balls with the diameter of 3mm into the tank, packaging in an argon glove box, placing in a ball mill, and performing mechanical ball milling treatment for 12 hours; wherein the rotation speed of the ball mill is 400rpm. The particle size of the phosphorus simple substance after ball milling is 300-500 nm.
Firstly, 100mg of freshly prepared ball-milled phosphorus anode material, a conductive agent (carbon black) and a binder (PVDF) are mixed according to a mass ratio of 8:1:1, N-methyl pyrrolidone (NMP) is used as a dispersion liquid, magnetic stirring is carried out for 12 hours at 30 ℃ to obtain uniformly mixed electrode slurry, the electrode slurry is uniformly coated on the surface of copper foil through an automatic coating machine, vacuum drying is carried out for 12 hours at 70 ℃, and the electrode slurry is cut into 12mm round electrode slices, so that a common phosphorus-based anode is obtained.
In order to obtain the phosphorus-based negative electrode plate with the in-situ oxidation layer, the material needs to be placed in air for 1 day to perform in-situ oxidation, the humidity RH is controlled to be 80%, and the temperature T is controlled to be 25 ℃. And then, drying the phosphorus-based negative electrode after in-situ oxidation in a vacuum oven for 12 hours to remove trace water on the surface of the in-situ oxidized phosphorus-based negative electrode, thereby obtaining the phosphorus-based negative electrode with the in-situ oxidation layer.
In a glove box filled with argon, the phosphorus-based negative electrode with the surface oxide layer is used as a working electrode, and a metal lithium sheet is used as a counter electrode, wherein 100 mu L of 1mol/L LiPF is added based on 1mg of the mass of the electrode material (i.e. the mass of the electrode sheet with the copper foil removed) 6 The ethylene carbonate/dimethyl carbonate (EC/DMC) electrolyte of (a) was normally assembled into a button cell having a CR2032 type specification using a polypropylene separator as a separator, and was allowed to stand at 25 ℃ for 12 hours. The rest process and the subsequent formation and circulation processes can carbonize the electrolyte to form the phosphorus-based negative electrode with the surface oxide layer and the carbonized layerAnd (5) a pole.
The lithium ion half-cell is subjected to constant-current charge and discharge test, the test system is a Wuhan blue electric cell test system, the test environment temperature is 28 ℃, and the cell is subjected to small-current activation (0.025 A.g) -1 (3 turns)), the test current density of the lithium ion half cell is 0.26 A.g -1 。
Capacity statistics table of lithium/sodium/potassium ion half-cell
(1) Examples 1 to 7 were lithium/sodium/potassium ion half-cells prepared from phosphorus-based negative electrode materials containing oxide layers and carbide layers obtained by powder oxidation, and the capacities of the lithium/sodium/potassium ion half-cells obtained in examples 1 to 7 and comparative examples 1 to 8 were counted, respectively, and the results are shown in table 2.
Table 2 statistics of the capacities of the lithium/sodium/potassium ion half-cells obtained in examples 1 to 7 and comparative examples 1 to 8
/>
Note that: the capacity retention rate in table 2 is calculated from the specific discharge capacity at 150 weeks of the cycle versus the specific capacity at the fourth week of the cycle.
As can be seen from the above table, the capacity retention rate shows a tendency to gradually increase with a gradual increase in the oxidation degree and carbonization degree. In examples 1 to 7, in the humidity range defined by the present invention, as the oxidation degree increases, the carbonization degree also increases, and the capacity retention rate gradually increases. Comparative examples 1 to 7 are half cells obtained from a phosphorus-based negative electrode material containing no oxide layer and no carbonized layer, and it can be seen from the above table that the capacity retention rates of examples 1 to 7 are far higher than those obtained in comparative examples 1 to 7, which means that the oxide layer and carbonized layer on the surface of the phosphorus core significantly improve the cycle performance of the cell. The relative humidity in comparative example 8 was outside the range defined by the present invention, and the first week reversible specific capacity and capacity retention rate were significantly lowered because too high humidity caused the oxide layer to absorb water, thereby losing the carbonization function, resulting in deterioration of electrochemical performance. The data show that the oxidation degree and the relative humidity jointly determine the carbonization degree, thereby determining the cycle performance of the battery, and only when the oxidation degree and the relative humidity are within the limit of the invention, the synergistic effect can be better exerted, and the organic matters are carbonized more effectively, so that the cycle performance of the battery is improved.
FIG. 5 is a ratio performance comparison of an electrode prepared by a powder oxidation process and an electrode prepared from unoxidized powder. As can be seen from FIG. 5, the electrochemical properties of the electrodes prepared by the powder oxidation method (examples 1,3,5 and 6) are significantly better than those of the unoxidized powder (comparative example 2), especially at 1.3, 2.6, 5.2 A.g -1 Is present at a large current density. At the same time, when the current density is returned to 0.26 A.g -1 The specific capacity and stability of the electrode prepared by the powder oxidation method are also significantly better than those of the unoxidized powder.
(2) The capacities of the lithium ion half-cells obtained in examples 8 to 12 and comparative examples 9 to 12 using the pole piece oxidation method were counted, and the results are shown in Table 3.
Table 3 statistical tables of capacities of lithium ion half batteries obtained in examples 8 to 12 and comparative examples 9 to 12
/>
As can be seen from table 3: in examples 8 to 12, by controlling the relative humidity to be within the range defined in the present invention, the capacity retention rate was increased as the oxidation degree was increased. Comparative examples 9-11 are lithium ion half-cells prepared from phosphorus-based negative electrode without oxide layer, and the capacity retention rate is much lower than that of examples 8-12, which indicates that the presence of oxide layer on the electrode surface significantly improves the cycle performance of the cell. The relative humidity in comparative example 12 was outside the range defined by the present invention, and the capacity retention ratio obtained was significantly lowered, which was far lower than that of examples 8 to 12, because the excessive humidity caused the oxide layer on the electrode surface to absorb water, and thus lost the carbonization function, resulting in the deterioration of electrochemical properties. This means that both the degree of oxidation and the relative humidity are within the limits of the present invention to effect carbonization and thereby increase the capacity retention of the battery.
Fig. 6 is a graph showing the rate performance of assembled lithium ion half-cells at different current densities for phosphorus-based negative electrodes prepared by a pole piece oxidation process (example 8) and a pole piece that has not been oxidized (comparative example 9). As can be seen from FIG. 6, the electrochemical performance of the electrode prepared by the electrode sheet oxidation method is significantly better than that of the unoxidized electrode sheet, especially at 1.3 A.g -1 、2.6A·g -1 、5.2A·g -1 Is present at a large current density. At the same time, when the current density is returned to 0.26 A.g -1 The specific capacity and stability of the electrode prepared by the pole piece oxidation method are obviously better than those of unoxidized powder. Indicating that the presence of the oxide and carbide layers can significantly enhance the electrochemical performance of the electrode.
Fig. 7 is the rate performance of the phosphorus-based negative electrode prepared in comparative example 12 assembled into a lithium ion half cell at different current densities. As can be seen from the figure, at 2.6A.g -1 、5.2A·g -1 At a large current density, the specific capacity of the electrode of comparative example 12 approaches 0; in addition, when the current density is returned to 0.26 A.g -1 At this time, the electrode of comparative example 12 showed a tendency to decrease in specific capacity and poor stability, because too high humidity would cause the oxide layer on the electrode surface to absorb water, thereby losing carbonization function and causing deterioration of electrochemical performance.
As can be seen from the above examples 1 to 12 and comparative examples 1 to 12, after the surface oxide layer and the carbonization layer are introduced on the surfaces of the phosphorus negative electrode material and the phosphorus-based electrode, the electron conductivity of the electrode can be improved, the SEI with high ion conductivity can be induced to be formed, and the cycle stability and the rate capability of the phosphorus negative electrode can be remarkably improved.
While the foregoing describes the embodiments of the present invention, it is not intended to limit the scope of the present invention, and on the basis of the technical solutions of the present invention, various modifications or variations may be made by those skilled in the art without the need for inventive labor.
Claims (33)
1. The phosphorus-based anode material is characterized by comprising a phosphorus core, an in-situ generated oxide layer on the surface of the phosphorus core and an in-situ generated carbonized layer;
the in situ generated oxide layer contains P x O y X is more than 0 and less than or equal to 2, and y is more than 0 and less than or equal to 5; the oxidation degree is 10-70% in terms of oxygen content, wherein the oxygen content refers to a mass percentage of oxygen atoms relative to the total mass of oxygen atoms and phosphorus atoms;
the carbonization layer generated in situ is a partially carbonized organic matter; the carbonization degree is 5% -50%.
2. The phosphorus-based anode material of claim 1, wherein the degree of oxidation is 35% to 50%; and/or, the carbonization degree is 30% -46%;
Preferably, the phosphorus core is elemental phosphorus;
more preferably, the elemental phosphorus contains one or more of red phosphorus, black phosphorus, violet phosphorus, blue phosphorus, green phosphorus and fibrous phosphorus.
3. The phosphorus-based anode material according to claim 1 or 2, wherein the organic substance is selected from an organic substance for a binder and/or an organic substance for a dispersion.
4. The phosphorus-based anode material according to claim 3, wherein the binder organic matter contains one or more of polyvinylidene fluoride, styrene-butadiene rubber, polytetrafluoroethylene, butyl rubber, epoxy resin, polyacrylic acid, polyacrylonitrile, polyimide, and polyethyleneimine;
preferably, the organic matters for the binder are selected from one or more than two of butyl rubber, polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid, styrene-butadiene rubber, polyacrylonitrile and epoxy resin;
more preferably, the organic matter for the binder is one or more selected from styrene-butadiene rubber, polyacrylic acid and epoxy resin.
5. The phosphorus-based anode material according to claim 3 or 4, wherein the dispersion liquid contains one or more of N-methylpyrrolidone, dimethylacetamide, dimethylformamide, N-methylpyrrole, dimethylsulfoxide, acetone, tetrahydrofuran, dimethylether, ethanol, and acetonitrile;
Preferably, the organic matters for the dispersion liquid are selected from one or more than two of N-methyl pyrrolidone, dimethylformamide, N-methyl pyrrole, ethanol, dimethyl sulfoxide and acetone;
more preferably, the organic matter for dispersion is one or more selected from the group consisting of N-methylpyrrolidone, ethanol and dimethylacetamide.
6. A method for producing the phosphorus-based anode material according to any one of claims 1 to 5, comprising the steps of:
(1) Placing the phosphorus core material in an atmosphere containing oxygen for oxidation reaction, and generating an oxide layer on the surface of the phosphorus core material in situ to obtain a phosphorus-based material with the oxide layer on the surface;
(2) And (3) placing the phosphorus-based material containing the oxide layer obtained in the step (1) in an organic matter for a binder and an organic matter for dispersion liquid for in-situ carbonization reaction to obtain the phosphorus-based anode material containing the oxide layer and the carbonized layer on the surface.
7. The method for producing a phosphorus-based anode material according to claim 6, wherein in the step (1), the particle diameter of the phosphorus core material is 10nm to 50 μm;
preferably, the particle size of the phosphorus core material is 100 nm-1 μm;
more preferably, the particle size of the phosphor core material is 100nm to 800nm.
8. The method for producing a phosphorus-based anode material according to claim 6 or 7, wherein in the step (1), the oxidation is carried out by allowing a phosphorus core material to stand for t days in an atmosphere containing oxygen for an oxidation reaction, wherein the standing time t is 0.5 to 15 days;
preferably, the standing time t is 3-15 days;
more preferably, the time t is from 5 to 15 days;
further preferably, the temperature of the oxidation reaction is 10 to 40 ℃.
9. The production method of a phosphorus-based anode material according to any one of claims 6 to 8, wherein in the step (1), the volume fraction V of oxygen in the oxygen-containing atmosphere is 5% to 100%;
preferably, the volume fraction V of oxygen in the oxygen-containing atmosphere is 15-98%;
more preferably, the volume fraction V of oxygen in the oxygen-containing atmosphere is 21% to 95%.
10. The production method of a phosphorus-based anode material according to any one of claims 6 to 9, wherein in the step (1), the relative humidity RH of the oxidation reaction is 0 to 50% and does not contain 0;
preferably, the relative humidity RH of the oxidation reaction is 2% -40%;
more preferably, the relative humidity RH of the oxidation reaction is 5% to 30%.
11. The production method of a phosphorus-based anode material according to any one of claims 6 to 10, wherein in the step (2), the carbonization reaction time t is 5min to 24h;
And/or the carbonization reaction temperature T is 10-90 ℃; preferably, the temperature T of the carbonization reaction is 25 to 80 ℃.
12. The method for producing a phosphorus-based anode material according to any one of claims 6 to 11, wherein in step (2), first, an organic substance for a binder is dispersed in an organic substance for dispersion to prepare a solution having a mass percentage of the organic substance for a binder of 1 to 15%, preferably a solution having a mass percentage of 1 to 8%; then adding the phosphorus-based anode material containing the oxide layer and the conductive agent obtained in the step (1) to perform in-situ carbonization reaction;
preferably, the mass percentage of the phosphorus-based anode material containing the oxide layer is 60% -95%, the mass percentage of the conductive agent is 2.5% -20%, and the mass percentage of the organic matter for the binder is 2.5% -20%.
13. A phosphorus-based anode material, characterized by being prepared by the method for preparing a phosphorus-based anode material according to any one of claims 6 to 12.
14. A phosphorus-based composite electrode, characterized in that the phosphorus-based composite electrode contains the phosphorus-based anode material according to any one of claims 1 to 5 or the phosphorus-based anode material according to claim 13, and a conductive agent and a binder.
15. A lithium ion battery comprising the phosphorus-based composite electrode of claim 14 and an electrolyte;
preferably, the positive electrode material in the lithium ion battery is selected from one or a combination of more than two of lithium cobaltate, lithium nickelate, lithium manganate, lithium nickelate aluminate, lithium manganate, lithium iron phosphate, lithium cobalt phosphate, lithium manganese phosphate, lithium vanadium phosphate and Prussian blue in any proportion.
16. A sodium ion battery comprising the phosphorus-based composite electrode of claim 14 and an electrolyte;
preferably, the positive electrode material in the sodium ion battery is selected from one or a combination of more than two of sodium nickel manganese oxide, sodium iron sulfate, sodium iron phosphate, sodium iron fluorophosphate, sodium vanadium phosphate, sodium vanadium fluorophosphate and Prussian blue in any proportion.
17. A potassium ion battery comprising the phosphorus-based composite electrode of claim 14 and an electrolyte;
preferably, the positive electrode material in the potassium ion battery is selected from one or a combination of more than two of lithium potassium cobaltate, potassium manganate, potassium vanadium phosphate and Prussian blue in any proportion.
18. Use of the lithium ion battery of claim 15, the sodium ion battery of claim 16 or the potassium ion battery of claim 17 in the energy field;
preferably, the lithium ion battery of claim 15, the sodium ion battery of claim 16 or the potassium ion battery of claim 17 is used in the field of electric vehicles, the field of mobile power sources and the field of energy storage power stations.
19. The phosphorus-based composite electrode is characterized by comprising a phosphorus-based negative electrode, an oxide layer formed by in-situ oxidation of the surface of the phosphorus-based negative electrode and a carbonization layer formed by in-situ carbonization;
the in situ generated oxide layer contains P x O y X is more than 0 and less than or equal to 2, and y is more than 0 and less than or equal to 5; the oxidation degree is 5 to 50% in terms of oxygen content, wherein the oxygen content refers to a mass percentage of oxygen atoms relative to the total mass of oxygen atoms, phosphorus atoms and carbon atoms; the carbon atom refers to a carbon atom in a carbon material as a conductive agent before in-situ carbonization, which is contained in the phosphorus-based anode;
the in-situ generated carbonization layer is a partially carbonized organic matter.
20. The phosphorus-based composite electrode according to claim 19, wherein the organic matter is selected from organic matters for an electrolyte;
Preferably, the organic matter for the electrolyte is selected from one or more than two of esters, ethers, sulfones and nitrile solvents;
more preferably, the ester solvent is one or more of ethylene carbonate, diethyl carbonate, polycarbonate, dimethyl carbonate, methylethyl carbonate, propylene carbonate, ethyl chlorocarbonate, ethyl propionate and propyl propionate;
and/or the ether solvent is one or more than two of ethylene glycol dimethyl ether, 1, 3-dioxolane and diglyme;
and/or the sulfone solvent is sulfolane and/or dimethyl sulfoxide;
and/or, the nitrile solvent is succinonitrile and/or adiponitrile;
more preferably, the organic matter for the electrolyte is ethylene carbonate, diethyl carbonate, ethylene glycol dimethyl ether and/or dimethyl sulfoxide.
21. A method of preparing the phosphorus-based composite electrode of claim 19 or 20, comprising the steps of:
(1) Uniformly mixing a phosphorus core material, a carbon material serving as a conductive agent and a binder, adding a dispersion liquid, uniformly mixing, coating on the surface of a metal foil, and drying to obtain a phosphorus-based negative electrode;
(2) Placing the phosphorus-based negative electrode obtained in the step (1) in an atmosphere containing oxygen for oxidation reaction, and generating an oxide layer on the surface of the phosphorus-based negative electrode in situ to obtain the phosphorus-based negative electrode with the surface containing the oxide layer;
(3) And (3) placing the phosphorus-based negative electrode with the surface containing the oxide layer obtained in the step (2) into an electrolyte organic matter for in-situ carbonization reaction to obtain the phosphorus-based composite electrode.
22. The method for producing a phosphorus-based composite electrode according to claim 21, wherein in the step (1), the phosphorus core material is elemental phosphorus; the simple substance phosphorus is selected from one or more than two of red phosphorus, black phosphorus, purple phosphorus, blue phosphorus, green phosphorus and fiber phosphorus;
the particle size of the phosphorus core material is 10 nm-50 mu m;
preferably, the particle size of the phosphorus core material is 100 nm-1 μm;
more preferably, the particle size of the phosphor core material is 300nm to 800nm.
23. The method for producing a phosphorus-based composite electrode as claimed in claim 21 or 22, wherein in the step (1), the carbon material as the conductive agent is one or more selected from carbon black, acetylene black, graphite, graphene, carbon nanotubes, porous carbon, ketjen black, carbon fibers, amorphous carbon, carbon nano/microspheres and pitch-cracked carbon.
24. The method for producing a phosphorus-based composite electrode as claimed in any one of claims 21 to 23, wherein in the step (2), the oxidation is carried out by allowing a phosphorus core material to stand for t days in an atmosphere containing oxygen, wherein the standing time t is: 0.5 to 15 days;
Preferably, the time t of placement is: 2-15 days;
more preferably, the temperature of the oxidation reaction is 10 to 40 ℃.
25. The method for producing a phosphorus-based composite electrode as claimed in any one of claims 21 to 24, wherein in the step (2), the volume fraction V of oxygen in the oxygen-containing atmosphere is: 5% -100%;
preferably, the volume fraction V of oxygen in the oxygen-containing atmosphere is: 15% -98%;
more preferably, the volume fraction V of oxygen in the oxygen-containing atmosphere is 21% to 95%.
26. The method for producing a phosphorus-based composite electrode as claimed in any one of claims 21 to 25, wherein in the step (2), the relative humidity RH of the oxidation reaction is: 0 to 50%, excluding 0;
preferably, the relative humidity RH of the oxidation reaction is: 1% -45%;
more preferably, the relative humidity RH of the oxidation reaction is: 2% -30%.
27. The method for producing a phosphorus-based composite electrode as claimed in any one of claims 21 to 26, wherein in the step (3), the time of the carbonization reaction is t: 5 min-24 h;
more preferably, the temperature T of the carbonization reaction is 20 to 40 ℃.
28. The method for producing a phosphorus-based composite electrode according to any one of claims 21 to 27, wherein in the step (3), the phosphorus-based negative electrode sheet having an oxide layer on the surface obtained in the step (2) is placed in an organic material for an electrolyte to undergo a carbonization reaction;
Preferably, the weight of the phosphorus-based anode material on the metal foil per square centimeter is 1-2 mg;
preferably, the volume of the organic matters for the electrolyte solution corresponding to each milligram of the phosphorus-based negative electrode material on the phosphorus-based negative electrode plate is 50-300 mu L.
29. A phosphorus-based composite electrode, characterized in that the phosphorus-based composite electrode is prepared by the method for preparing a phosphorus-based composite electrode according to any one of claims 21 to 28.
30. A lithium ion battery comprising the phosphorus-based composite electrode of claim 19, 20 or 29 and an electrolyte; wherein the electrolyte and the electrolyte organic matter are selected from the same substances;
preferably, the positive electrode material in the lithium ion battery is selected from one or a combination of more than two of lithium cobaltate, lithium nickelate, lithium manganate, lithium nickelate aluminate, lithium manganate, lithium iron phosphate, lithium cobalt phosphate, lithium manganese phosphate, lithium vanadium phosphate and Prussian blue in any proportion.
31. A sodium ion battery comprising the phosphorus-based composite electrode of claim 19, 20 or 29 and an electrolyte; wherein the electrolyte and the electrolyte organic matter are selected from the same substances;
Preferably, the positive electrode material in the sodium ion battery is selected from one or a combination of more than two of sodium nickel manganese oxide, sodium iron sulfate, sodium iron phosphate, sodium iron fluorophosphate, sodium vanadium phosphate, sodium vanadium fluorophosphate and Prussian blue in any proportion.
32. A potassium ion battery comprising the phosphorus-based composite electrode of claim 19, 20 or 29 and an electrolyte; wherein the electrolyte and the electrolyte organic matter are selected from the same substances;
preferably, the positive electrode material in the potassium ion battery is selected from one or a combination of more than two of lithium potassium cobaltate, potassium manganate, potassium vanadium phosphate and Prussian blue in any proportion.
33. Use of the lithium ion battery of claim 30, the sodium ion battery of claim 31 or the potassium ion battery of claim 32 in the energy field;
preferably, the lithium ion battery of claim 30, the sodium ion battery of claim 31 or the potassium ion battery of claim 32 is used in the fields of electric vehicles, mobile power sources and energy storage power stations.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211021144.6A CN117673282A (en) | 2022-08-24 | 2022-08-24 | Phosphorus-based negative electrode material, phosphorus-based composite electrode, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211021144.6A CN117673282A (en) | 2022-08-24 | 2022-08-24 | Phosphorus-based negative electrode material, phosphorus-based composite electrode, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117673282A true CN117673282A (en) | 2024-03-08 |
Family
ID=90077349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211021144.6A Pending CN117673282A (en) | 2022-08-24 | 2022-08-24 | Phosphorus-based negative electrode material, phosphorus-based composite electrode, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117673282A (en) |
-
2022
- 2022-08-24 CN CN202211021144.6A patent/CN117673282A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | A lightweight multifunctional interlayer of sulfur–nitrogen dual-doped graphene for ultrafast, long-life lithium–sulfur batteries | |
| Lin et al. | Lithium–sulfur batteries: from liquid to solid cells | |
| Zhang et al. | Encapsulating sulfur into a hybrid porous carbon/CNT substrate as a cathode for lithium–sulfur batteries | |
| Li et al. | A hydrophilic separator for high performance lithium sulfur batteries | |
| Huang et al. | Calix [6] quinone as high-performance cathode for lithium-ion battery | |
| KR20120010211A (en) | Porous silicon based alloy, method of preparing the same, and negative active material for rechargeable lithium battery and rechargeable lithium battery including the same | |
| Li et al. | Enhancing the kinetics of lithium–sulfur batteries under solid-state conversion by using tellurium as a eutectic accelerator | |
| KR102065256B1 (en) | Silicone based negative active material, preparing method of the same and lithium ion secondary battery including the same | |
| KR20200058644A (en) | Electrode composite conducting agent for lithium battery, electrode for lithium battery, preparing method thereof, and lithium battery including the same | |
| CN111342018B (en) | Carbon-coated lithium-containing transition metal phosphate positive electrode material and preparation method thereof | |
| CN110635116A (en) | Lithium ion battery cathode material, preparation method thereof, cathode and lithium ion battery | |
| CN114552125B (en) | Nondestructive lithium supplement composite diaphragm and preparation method and application thereof | |
| CN112689919A (en) | Negative electrode active material, and electrochemical device and electronic device using same | |
| KR20120092918A (en) | Polymer composite electrolyte for rechargeable lithium battery and rechargeable lithium battery including same | |
| CN116683017A (en) | High-energy-density sodium-free negative electrode sodium battery | |
| Jin et al. | Enhancing the performance of sulfurized polyacrylonitrile cathode by in-situ wrapping | |
| CN114730855B (en) | Electrochemical device and electronic device | |
| Lou et al. | Graphite-like structure of disordered polynaphthalene hard carbon anode derived from the carbonization of perylene-3, 4, 9, 10-tetracarboxylic dianhydride for fast-charging lithium-ion batteries | |
| CN117559013A (en) | Lithium supplementing agent composite material and preparation method and application thereof | |
| CN112768664A (en) | Preparation method of ruthenium-doped lithium iron phosphate composite positive electrode material | |
| Li et al. | Effect of Ether-Based and Carbonate-Based Electrolytes on the Electrochemical Performance of Li–S Batteries | |
| Hou et al. | Improvement Strategies toward Stable Lithium‐Metal Anodes for High‐Energy Batteries | |
| CN114497507A (en) | Quick-filling graphite composite material and preparation method thereof | |
| CN117673282A (en) | Phosphorus-based negative electrode material, phosphorus-based composite electrode, and preparation method and application thereof | |
| Dong et al. | Fabrication of Uniform Fe3O4 Nanocubes Derived from Prussian Blue and Enhanced Performance for Lithium Storage Properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |