CN111354934B - Silicon-based negative electrode material and application thereof - Google Patents
Silicon-based negative electrode material and application thereof Download PDFInfo
- Publication number
- CN111354934B CN111354934B CN202010209336.4A CN202010209336A CN111354934B CN 111354934 B CN111354934 B CN 111354934B CN 202010209336 A CN202010209336 A CN 202010209336A CN 111354934 B CN111354934 B CN 111354934B
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- China
- Prior art keywords
- phthalocyanine
- silicon
- copper
- negative electrode
- lithium battery
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 145
- 239000010703 silicon Substances 0.000 title claims abstract description 145
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 57
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 55
- -1 phthalocyanine compound Chemical class 0.000 claims abstract description 41
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 60
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims description 31
- 239000010405 anode material Substances 0.000 claims description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical compound N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 claims description 9
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 claims description 5
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- LZGCHNNAWUTUOV-UHFFFAOYSA-N anthracene copper Chemical compound [Cu].C1=CC=CC2=CC3=CC=CC=C3C=C12 LZGCHNNAWUTUOV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 claims description 3
- RLDWIFDMZUBMGW-UHFFFAOYSA-N 29h,31h-phthalocyanine, disodium salt Chemical compound [Na+].[Na+].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 RLDWIFDMZUBMGW-UHFFFAOYSA-N 0.000 claims description 3
- HUVXQFBFIFIDDU-UHFFFAOYSA-N aluminum phthalocyanine Chemical compound [Al+3].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 HUVXQFBFIFIDDU-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- HQQKMOJOCZFMSV-UHFFFAOYSA-N dilithium phthalocyanine Chemical compound [Li+].[Li+].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 HQQKMOJOCZFMSV-UHFFFAOYSA-N 0.000 claims description 3
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- LBAIJNRSTQHDMR-UHFFFAOYSA-N magnesium phthalocyanine Chemical compound [Mg].C12=CC=CC=C2C(N=C2NC(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2N1 LBAIJNRSTQHDMR-UHFFFAOYSA-N 0.000 claims description 3
- GIORIKOBPFKYKT-UHFFFAOYSA-N copper;naphthalene Chemical compound [Cu].C1=CC=CC2=CC=CC=C21 GIORIKOBPFKYKT-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000000151 deposition Methods 0.000 description 11
- 239000007888 film coating Substances 0.000 description 10
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- 229920000573 polyethylene Polymers 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
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- 238000010438 heat treatment Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
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- 239000005543 nano-size silicon particle Substances 0.000 description 4
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- 239000000843 powder Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- IVUBJNPDPBDVLT-UHFFFAOYSA-N 2,15,28,41,53,55-hexaza-54,56-diazanidatridecacyclo[40.10.1.13,14.116,27.129,40.04,13.06,11.017,26.019,24.030,39.032,37.043,52.045,50]hexapentaconta-1,3,5,7,9,11,13,15,17,19,21,23,25,27(55),28,30,32,34,36,38,40,42(53),43,45,47,49,51-heptacosaene oxovanadium(2+) Chemical compound [V+2]=O.[N-]1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)[N-]3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 IVUBJNPDPBDVLT-UHFFFAOYSA-N 0.000 description 2
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
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- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- YRZZLAGRKZIJJI-UHFFFAOYSA-N oxyvanadium phthalocyanine Chemical compound [V+2]=O.C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 YRZZLAGRKZIJJI-UHFFFAOYSA-N 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NURIJECXIAPSAM-UHFFFAOYSA-N silicon phthalocyanine dichloride Chemical compound N1=C(C2=CC=CC=C2C2=NC=3C4=CC=CC=C4C(=N4)N=3)N2[Si](Cl)(Cl)N2C4=C(C=CC=C3)C3=C2N=C2C3=CC=CC=C3C1=N2 NURIJECXIAPSAM-UHFFFAOYSA-N 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
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- 150000002258 gallium Chemical class 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
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- 238000009830 intercalation Methods 0.000 description 1
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- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
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- 238000005457 optimization Methods 0.000 description 1
- VVOPUZNLRVJDJQ-UHFFFAOYSA-N phthalocyanine copper Chemical compound [Cu].C12=CC=CC=C2C(N=C2NC(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2N1 VVOPUZNLRVJDJQ-UHFFFAOYSA-N 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
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- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 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
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Abstract
The invention provides a silicon-based negative electrode material and application thereof, wherein the silicon-based negative electrode material comprises a silicon-based core and a shell layer, and at least part of the surface of the silicon-based core is coated by the shell layer; the shell layer comprises a phthalocyanine compound. The silicon-based negative electrode material is used in a lithium battery, and the cycle performance and the charge-discharge rate performance of the lithium battery can be remarkably improved. Meanwhile, the internal resistance of the lithium battery can be effectively reduced.
Description
Technical Field
The invention relates to a negative electrode material, in particular to a silicon-based negative electrode material and application thereof, and belongs to the technical field of lithium batteries.
Background
Lithium ion batteries have the characteristics of high energy density, long cycle life and environmental friendliness, have been widely used in electronic products such as mobile communication devices, notebook computers, digital cameras and the like, and gradually play a role in the fields of electric vehicles and energy storage. The negative electrode material is one of the key materials of the lithium ion battery, the most applied commercial lithium ion battery is graphite, the theoretical specific capacity of the graphite is low (372mAh/g), and the graphite cannot meet the requirement of the high-energy-density lithium ion battery at present. The theoretical specific capacity of the silicon-based negative electrode material can reach 4200mAh/g, so that the silicon-based negative electrode material can replace a graphite negative electrode to remarkably improve the energy density of the battery, and is a next-generation negative electrode material with a good application prospect.
However, the silicon-based material undergoes a large volume change during the process of lithium intercalation and deintercalation, resulting in poor cycle performance and low charge-discharge rate performance.
Disclosure of Invention
Aiming at the defects, the invention provides the silicon-based negative electrode material, and the silicon-based negative electrode material is used in the lithium battery through improving the structure of the silicon-based negative electrode material, so that the cycle performance and the charge-discharge rate performance of the lithium battery can be obviously improved. Meanwhile, the internal resistance of the lithium battery can be effectively reduced, and the serious influence on the electrical performance and the safety performance of the lithium battery due to excessive heat release in the long-term use process of the lithium battery is avoided.
The invention also provides a negative electrode which comprises the silicon-based negative electrode material and can remarkably improve the cycle performance and the charge-discharge rate performance of a lithium battery. Meanwhile, the internal resistance of the lithium battery can be effectively reduced, and the serious influence on the electrical performance and the safety performance of the lithium battery due to excessive heat release in the long-term use process of the lithium battery is avoided.
The invention also provides a lithium battery which comprises the negative electrode, so that the lithium battery has excellent cycle performance, rate capability and safety performance.
The invention provides a silicon-based anode material, which comprises a silicon-based core and a shell, wherein at least part of the surface of the silicon-based core is coated by the shell;
the shell layer comprises a phthalocyanine compound.
The silicon-based anode material as described above, wherein, the phthalocyanine compound is selected from at least one of phthalocyanine, perfluorophthalocyanine, polyphthalocyanine, naphthalocyanine, anthracyanine, iron phthalocyanine, copper phthalocyanine, zinc phthalocyanine, magnesium phthalocyanine, cobalt phthalocyanine, tin phthalocyanine, aluminum phthalocyanine, disodium phthalocyanine, dilithium phthalocyanine, dipotassium phthalocyanine, nickel phthalocyanine, poly (copper phthalocyanine), indium phthalocyanine, perfluorozinc phthalocyanine, iron chlorophthalocyanine, 2, 3-naphthalocyanine aluminum chloride, 2, 3-naphthalocyanine cobalt, sulfonated cobalt phthalocyanine, silicon phthalocyanine dichloride, chloro gallium phthalocyanine, oxytitanium phthalocyanine, vanadyl phthalocyanine, perfluorocopper phthalocyanine, nickel phthalocyanine tetrasulfonic acid tetrasodium salt, manganese phthalocyanine chloride, zinc phthalocyanine tetrasulfonate, vanadyl 2, 3-naphthalocyanine, 2, 3-naphthalocyanine tin phthalocyanine, polychlorinated copper phthalocyanine, silver phthalocyanine, gallium phthalocyanine, copper phthalocyanine chloride, copper naphthalocyanine, anthracene phthalocyanine copper phthalocyanine, and doped copper phthalocyanine.
The silicon-based negative electrode material is characterized in that the phthalocyanine compound is a metal phthalocyanine compound.
The silicon-based negative electrode material as described above, wherein the metal peptoide cyanine compound is at least one selected from copper phthalocyanine, zinc phthalocyanine, poly (copper phthalocyanine), indium phthalocyanine, gallium phthalocyanine, perfluoro zinc phthalocyanine, perfluoro copper phthalocyanine, polychlorinated copper phthalocyanine, silver phthalocyanine, chlorinated copper phthalocyanine, naphthalocyanine copper phthalocyanine, anthracene copper phthalocyanine, and doped copper phthalocyanine.
The silicon-based negative electrode material comprises a shell layer and a shell layer, wherein the shell layer is 0.01-2% of the silicon-based negative electrode material by mass.
The silicon-based anode material is characterized in that the silicon-based core is a carbon-silicon composite material.
The silicon-based anode material as described above, wherein the silicon-based core is silicon or an oxide of silicon.
The silicon-based anode material as described above, wherein the silicon-based core has an average size of 5nm to 10 μm.
The invention also provides a silicon-based negative electrode, which comprises the silicon-based negative electrode material.
The invention also provides a lithium battery, and the negative electrode of the lithium battery is the silicon-based negative electrode.
According to the silicon-based negative electrode material provided by the invention, the surface of the silicon-based core is specially improved and modified, and the silicon-based core is used as a negative electrode active material and applied to a lithium battery, so that the energy density of the battery can be obviously improved, the cycle performance and the charge-discharge rate performance of the lithium battery can be optimized, and the constant-current charge rate and the discharge capacity retention rate of the battery can be improved; in addition, the silicon-based negative electrode material can reduce the internal resistance of the battery and the internal resistance increase rate of the battery in the long-term circulation process, thereby avoiding safety accidents possibly caused by excessive heat release of the battery in the repeated charging process and negative influence on the related electrical performance.
The cathode provided by the invention comprises the silicon-based cathode material, so that the cycle performance, the charge-discharge rate performance and other electrical properties and safety performance of the lithium battery are improved.
The lithium battery provided by the invention comprises the negative electrode, so that the cycle performance, the charge-discharge rate performance and other electrical properties and safety performance of the lithium battery are remarkably improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a silicon-based anode material, which comprises a silicon-based core and a shell, wherein at least part of the surface of the silicon-based core is coated by the shell; the shell layer comprises phthalocyanine compounds.
The silicon-based core is a main body of the silicon-based negative electrode material, contains silicon element, has a certain shape, and can be granular, linear, flaky and the like.
The silicon-based negative electrode material comprises the silicon-based core and a shell layer, wherein the shell layer comprises a phthalocyanine compound and covers at least part of the outer surface of the silicon-based core in a wrapping manner. That is, the shell layer may be a continuous layer covering the entire outer surface of the silicon-based core, or may be a continuous layer covering a portion of the outer surface of the silicon-based core. Wherein the thickness of the clad layer may be uniform or non-uniform.
According to the technical scheme provided by the invention, the silicon-based negative electrode material is applied to the lithium battery, so that the energy density of the lithium battery is improved, and the lithium battery has good cycle performance and rate capability. The inventors have analyzed based on this phenomenon and considered that it is possible to: on one hand, the silicon-based inner core in the silicon-based negative electrode material has higher theoretical specific capacity compared with a graphite material, so that the energy density of the lithium battery is improved; on the other hand, the phthalocyanine compound in the shell layer has a conjugated pi-bond structure, so that the growth of lithium dendrites can be effectively inhibited in the process of repeatedly charging the lithium battery, the stability of the electrical property of the lithium battery is maintained, and the cycle performance of the lithium battery is good; the electronic conduction characteristic of the phthalocyanine compound is beneficial to realizing the optimization of the surface conductivity of the negative plate, thereby improving the rate capability of the lithium battery. In addition, the inventor also finds that the silicon-based negative electrode material can reduce the internal resistance of the lithium battery, and the internal resistance growth rate of the lithium battery is generally low after the lithium battery is cycled for a long time, so that the heat release of the lithium battery is not obvious in the long-term use process, and the potential safety hazard caused by excessive heat release is avoided.
The silicon-based core can be silicon or silicon oxide, such as silica, nano-silicon and silicon nanowires, or can be a silicon-carbon composite material, such as carbon-coated silica, carbon-coated nano-silicon, carbon-coated silicon nanowires and silicon-coated carbon materials.
In view of the easy expansion and poor conductivity of silicon materials, the silicon-carbon composite material is preferably used as the silicon-based core.
In one embodiment, silicon-based cores having an average size of 5nm to 10 μm may be selected. The average size here is in particular the D50 value measured with a malvern laser granulometer 3000.
The phthalocyanine-based compound of the present invention may be at least one of phthalocyanine, perfluorophthalocyanine, polyphthalocyanine, naphthalocyanine, anthracyanine, iron phthalocyanine, copper phthalocyanine, zinc phthalocyanine, magnesium phthalocyanine, cobalt phthalocyanine, tin phthalocyanine, aluminum phthalocyanine, disodium phthalocyanine, dilithium phthalocyanine, dipotassium phthalocyanine, nickel phthalocyanine, poly (copper phthalocyanine), indium phthalocyanine, perfluorozinc phthalocyanine, iron chlorophthalocyanine, 2, 3-naphthalocyanine aluminum chloride, 2, 3-naphthalocyanine cobalt, sulfonated phthalocyanine cobalt, silicon phthalocyanine dichloride, chlorinated gallium phthalocyanine, oxytitanium phthalocyanine, vanadyl phthalocyanine, perfluorocopper phthalocyanine, nickel phthalocyanine tetrasulfonic acid tetrasodium salt, manganese phthalocyanine chloride, zinc tetrasulfonate, vanadyl 2, 3-naphthalocyanine, tin naphthalocyanine, polychlorinated copper phthalocyanine, silver phthalocyanine, gallium phthalocyanine, copper phthalocyanine chloride, copper naphthalocyanine, anthracene phthalocyanine, and doped copper phthalocyanine.
When the metal phthalocyanine compound is selected, for example, at least one of copper phthalocyanine, zinc phthalocyanine, poly (copper phthalocyanine), indium phthalocyanine, gallium phthalocyanine, perfluorozinc phthalocyanine, perfluorocopper phthalocyanine, polychlorinated copper phthalocyanine, silver phthalocyanine, chlorinated copper phthalocyanine, naphthalocyanine copper phthalocyanine, anthracene copper phthalocyanine and doped copper phthalocyanine is more effective in improving the performance of the silicon-based negative electrode material.
In the implementation process of the invention, when the lithium battery selects different anode materials, electrolyte and the like, the final performance of the lithium battery is affected. Therefore, in general, in the case of the above-mentioned different positive electrode materials, electrolyte solutions, and the like, when the mass percentage of the shell layer in the silicon-based negative electrode material is 0.01 to 2%, the cycle performance and the charge-discharge rate performance of the lithium battery can be substantially improved to a large extent.
The silicon-based negative electrode material can be prepared by a method comprising the following steps of: and coating the material containing the phthalocyanine compound on at least part of the outer surface of the silicon-based core in a deposition or coating mode to obtain the silicon-based negative electrode material.
The deposition can be a vacuum evaporation deposition or a vacuum coating mode, and the coating can be obtained by preparing a phthalocyanine compound into a solution and soaking the silicon-based inner core into the solution.
In one embodiment, the phthalocyanine compound may be deposited on at least a portion of the surface of the silicon-based core by physical vapor deposition to obtain the silicon-based negative electrode material. Wherein the physical vapor deposition comprises one of vacuum evaporation deposition and vacuum coating.
In the implementation process of vacuum evaporation deposition, a multi-temperature-zone temperature-controlled vacuum tube furnace can be adopted to deposit the phthalocyanine compound on the surface of the silicon-based core, for example, a five-temperature-zone temperature-controlled vacuum tube furnace, the phthalocyanine compound is placed in an evaporation crucible and placed in the 1 st temperature zone of the tube furnace, then the silicon-based core is placed in the 3 rd temperature zone of the tube furnace, the temperature of the 1 st temperature zone is set to be 300-1200 ℃, and the 3 rd temperature zone is set to be 30-250 ℃ (the other temperature zones are not heated and controlled). Introducing inert gas (argon, helium and the like) into an air inlet of the tube furnace, controlling the gas flow to be 0.1-10 mL/min, starting a vacuum pump, and controlling the vacuum degree to be 1.0 multiplied by 10-4～1.0×10-1Pa, depositing for 0.1-4 h, then closing and heating, cooling to room temperature, and taking out the powderThe silicon-based negative electrode material is provided by the invention.
In the implementation process of vacuum coating, a vacuum coating machine can be adopted to deposit the phthalocyanine compound on the surface of the silicon-based inner core. Specifically, the phthalocyanine compound is placed in an evaporation crucible, and the silicon-based inner core is placed in a film coating area for film coating operation. The vacuum chamber is controlled to have a vacuum degree of 5.0X 10 and a deposition current of 40 to 180A-5～1.0×10-2Pa, and the film coating time is 0.01-4 h. And after the film coating is finished, closing and heating, and cooling to room temperature, and taking out powder to obtain the silicon-based negative electrode material.
In another embodiment, the silicon-based core is immersed in a phthalocyanine compound solution, and the solvent on the surface of the silicon-based core is removed to obtain the silicon-based negative electrode material.
Specifically, mixing the phthalocyanine compound with a solvent to obtain a solution, dipping the silicon-based core in the solution, taking out, and removing the solvent to obtain the silicon-based negative electrode material. The solvent used for preparing the solution in the present invention may be at least one selected from the group consisting of ethyl acetate, chloroform, dichloromethane, dichloroethane, ethylenediamine, acetic acid, ethanol, acetonitrile, isopropanol, acetone, and isopropanol. The concentration of the solution can be controlled to be 0.1-10 mmol/L. In order to ensure effective coating of the phthalocyanine compound on the surface of the silicon-based core, the impregnation time can be controlled to be generally 0.5 to 24 hours.
The invention also provides a silicon-based cathode which comprises the silicon-based cathode material.
Specifically, the silicon-based negative electrode material serving as an active material of the silicon-based negative electrode can be dispersed in a proper amount of deionized water solvent together with conductive carbon black, Styrene Butadiene Rubber (SBR) serving as a binder and sodium carboxymethyl cellulose (CMC) serving as a thickener according to a certain proportion, and the mixture is fully stirred and mixed to form uniform negative electrode slurry; and uniformly coating the negative electrode slurry on a negative electrode current collector, and drying, rolling and slitting to obtain the silicon-based negative electrode.
The invention also provides a lithium battery, and the negative plate of the lithium battery is the silicon-based negative electrode. Besides, the lithium battery also comprises a positive plate, a diaphragm and electrolyte.
The active material of the positive plate is not strictly limited, and can be a positive active material commonly used in the current lithium battery, such as at least one of lithium cobaltate, lithium nickelate, lithium manganate, nickel cobalt manganese ternary material, nickel cobalt aluminum ternary material, lithium iron phosphate (LFP), nickel lithium manganate, lithium-rich manganese-based material, and the like.
Specifically, in the operation, the at least one positive electrode active material, the conductive agent and the binder may be dispersed in an appropriate amount of solvent, and fully stirred and mixed to form a uniform positive electrode slurry; and uniformly coating the positive slurry on a positive current collector aluminum foil, and drying, rolling and slitting to obtain the positive plate.
The electrolyte selection is not strictly limited in the present invention, and may include one or more of the solvents commonly used in the current lithium battery electrolytes, and the electrolyte lithium salts commonly used in the current lithium ion electrolytes, such as: the solvent may be ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate (FEC), dimethyl carbonate (DMC), diethyl carbonate (DEC), difluoroethylene carbonate (DFEC), dipropyl carbonate, methylethyl carbonate (EMC), ethyl acetate, ethyl propionate, propyl acetate, propyl propionate, sulfolane, γ -butyrolactone, etc.; the lithium salt is selected from lithium hexafluorophosphate (LiPF)6) One or more of lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI).
The material selection of the diaphragm is not strictly limited, and the diaphragm can be a commonly used diaphragm material in the current lithium battery, such as one of a polypropylene diaphragm (PP), a polyethylene diaphragm (PE), a polypropylene/polyethylene double-layer composite film (PP/PE), a polyimide electrostatic spinning diaphragm (PI), a polypropylene/polyethylene/polypropylene three-layer composite film (PP/PE/PP), a cellulose non-woven fabric diaphragm and a diaphragm with a ceramic coating.
When the lithium battery is prepared, the positive plate, the diaphragm and the silicon-based negative plate are wound or laminated to obtain a bare cell, and the bare cell is packaged into an aluminum-plastic film bag which is formed in a stamping mode in advance. And (3) after the packaged battery is dried at 85 ℃, injecting the electrolyte into the dried battery, and finishing the preparation of the lithium battery after the battery is laid aside, formed and secondarily sealed.
The lithium battery provided by the invention has good specific capacity, cycle performance, charge-discharge rate performance and low internal resistance due to the silicon-based negative electrode.
The silicon-based anode material of the present invention is described in detail by specific examples below.
The reagents, materials and instruments used below are all conventional reagents, conventional materials and conventional instruments, and are commercially available, unless otherwise specified. Wherein the five-temperature-zone temperature-controlled vacuum tube furnace is an OTF-1200X-V-H4 model five-temperature-zone temperature-controlled vacuum tube furnace manufactured by Shenzhen, science and technology Limited, and the vacuum coating machine is a ZHD300 vacuum coating machine manufactured by Beijing Tai Kenuo science and technology Limited.
Examples 1 to 8
1-8, adopting a five-temperature-zone temperature-control vacuum tube furnace to deposit the phthalocyanine compound on the surface of the silicon-based core to prepare the silicon-based negative electrode material 1-8 #.
Specifically, the phthalocyanine compound is placed in an evaporation crucible and placed in a 1 st temperature zone of a tube furnace, then a silicon-based core is placed in a 3 rd temperature zone of the tube furnace, and the 1 st temperature zone and the 3 rd temperature zone are opened and set (the other temperature zones are not heated for temperature control). Introducing argon gas into an air inlet of the tube furnace, controlling the gas flow, starting a vacuum pump, controlling the vacuum degree, stopping heating after deposition, cooling to room temperature, and taking out the powder, namely the silicon-based negative electrode material. The specific process parameters are shown in Table 1.
Wherein, the mass fraction P ═ W of the shell layer in the silicon-based negative electrode material2-W1)/W2×100％，W2For the mass of the taken-out silicon-based anode material, W1The quality of the silicon-based inner core is put into the 3 rd temperature zone.
The size of the silicon-based inner core is the average size of the material, and is specifically the D50 value measured by a Malvern laser particle sizer 3000.
TABLE 1
Examples 9 to 16
Examples 9 to 16 silicon-based negative electrode materials 9 to 16 were prepared by depositing phthalocyanine compounds on the surface of a silicon-based core using a vacuum coater.
Specifically, the phthalocyanine compound is placed in an evaporation crucible, and the silicon-based inner core is placed in a film coating area for film coating operation. And after the film coating is finished, closing and heating, and cooling to room temperature, and taking out the powder to obtain the silicon-based negative electrode material. The specific process parameters are shown in Table 2.
Wherein, the mass fraction P ═ W of the shell layer in the silicon-based negative electrode material2-W1)/W2×100％，W2For the mass of the taken-out silicon-based anode material, W1Is the mass of the silicon-based core placed in the coating region.
The size of the silicon-based inner core is the average size of the material, and is specifically the D50 value measured by a Malvern laser particle sizer 3000.
TABLE 2
Example 17 example 24
Examples 17 to 24 silicon-based negative electrode materials 17 to 24 were prepared by depositing phthalocyanine-based compounds on the surface of a silicon-based core using a solution coating method.
And mixing the phthalocyanine compound with a solvent to prepare a solution, soaking the silicon-based core in the solution for a certain time, taking out the silicon-based core, and evaporating the solvent to dryness to obtain the silicon-based negative electrode material. The specific parameters are shown in Table 2.
Wherein, the mass fraction P ═ W of the shell layer in the silicon-based negative electrode material2-W1)/W2×100％，W2Is the mass of the silicon-based anode material, W1Is the mass of the silicon-based core.
The size of the silicon-based inner core is the average size of the material, and is specifically the D50 value measured by a Malvern laser particle sizer 3000.
TABLE 3
Examples 25 to 40
Examples 25 to 40 silicon-based negative electrode materials 25 to 40 were prepared by depositing phthalocyanine compounds on the surface of a silicon-based core using a vacuum coater.
Specifically, the phthalocyanine compound is placed in an evaporation crucible, and the silicon-based inner core is placed in a film coating area for film coating operation. And after the film coating is finished, closing and heating, and cooling to room temperature, and taking out the powder to obtain the silicon-based negative electrode material. The specific process parameters are shown in Table 4.
Wherein, the mass fraction P ═ W of the shell layer in the silicon-based negative electrode material2-W1)/W2×100％，W2For the mass of the taken-out silicon-based anode material, W1Is the mass of the silicon-based core placed in the coating region.
The size of the silicon-based inner core is the average size of the material, and is specifically the D50 value measured by a Malvern laser particle sizer 3000.
TABLE 4
Comparative examples 1a to 8a
The negative electrode materials of comparative examples 1a to 8a were, respectively, a 1:4 mixture of a silica having a particle size of 1 μm, a silica having a particle size of 10 μm and graphite, a carbon-coated silica having a particle size of 3 μm, a nano-silicon having a particle size of 5nm, a carbon-coated nano-silicon having a particle size of 30nm, a silicon nanowire having a particle size of 80nm, a carbon-coated silicon nanowire having a particle size of 100nm, and a silicon-carbon composite material having a particle size of 1 μm.
Test examples
The silicon-based negative electrode materials of the above examples and comparative examples were respectively prepared as negative electrode sheets according to the following methods:
adding 40 parts by mass of a silicon-based negative electrode material (or a mixed negative electrode material mixed with the silicon-based negative electrode material), 0.5 part by mass of a carbon black conductive agent, 0.5 part by mass of a carbon nanotube conductive agent, 0.5 part by mass of an SBR (styrene butadiene rubber) binder, 0.5 part by mass of a PAA (poly (acrylic acid)) binder and 58 parts by mass of deionized water into a double-planetary mixer, and stirring for 4 hours at a revolution speed of 100 revolutions per minute and a dispersion disc rotation speed of 2500 revolutions per minute to obtain negative electrode slurry. Coating the negative electrode slurry on the surface of a current collector through an extrusion type coating machine, fully drying the current collector in a drying oven at 110 ℃ for 0.5h, and adjusting coating parameters (the coating speed is 2-30 m/min, and the gap between a die head and a coating roll is 5-900 mu m) of the coating machine to obtain a required surface density numerical value (shown in a table 5); rolling the dried negative pole piece by a roller press, and adjusting the rolling pressure (adjusted within the range of 20-75 tons) to obtain a required pole piece compaction density numerical value (shown in Table 5); and finally, cutting the rolled negative plate into a finished negative plate for later use.
The prepared negative plate is matched with a positive plate (4.4V lithium cobalt oxide manufactured by Beijing Dangsheng materials science and technology Co., Ltd., the surface density of the plate is 20mg/cm2The compacted density of the pole piece is 4.16g/cm3) The lithium batteries 1 to 48 are prepared from a Polyethylene (PE) porous diaphragm (a wet diaphragm ND12 produced by Shanghai Enjie New Material science and technology Limited and having a thickness of 12 μm) and a commercially conventional lithium ion battery electrolyte (an electrolyte of type LBC445B33 produced by Shenzhen New Zealand science and technology Limited) by a conventional lithium ion battery preparation process, and are tested in the following way.
1. Cycle performance and rate performance
And (3) testing the cycle performance and the rate capability of the battery by referring to a test method in GB/T18287-2013 standard, wherein the cycle test conditions are as follows: 25 ℃ and 0.5C/0.5C (the upper limit voltage is set to 4.4V, and the lower limit voltage is set to 3.0V); the rate charging performance mainly considers the constant current charging ratio of 3C charging, and the rate discharging performance mainly considers the capacity retention rate of 3C discharging. The test results are shown in table 5.
2. Internal resistance of battery
And testing the initial internal resistance of the battery and the internal resistance after 100 cycles under the circulation condition by adopting an RBM-200 intelligent battery internal resistance tester of Shenzhen super thinking science and technology Limited. The test results are shown in table 5.
TABLE 5
As can be seen from Table 5: the silicon-based negative electrode material provided by the invention can improve the specific capacity of a lithium battery, and simultaneously has good cycle performance, rate performance and lower internal resistance.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. The silicon-based anode material is characterized by comprising a silicon-based core and a shell, wherein at least part of the surface of the silicon-based core is coated by the shell;
the shell layer comprises a phthalocyanine compound;
the phthalocyanine compound is selected from at least one of phthalocyanine, perfluorophthalocyanine, polyphthalocyanine, naphthalocyanine, anthracene phthalocyanine, iron phthalocyanine, copper phthalocyanine, zinc phthalocyanine, magnesium phthalocyanine, cobalt phthalocyanine, tin phthalocyanine, aluminum phthalocyanine, disodium phthalocyanine, dilithium phthalocyanine, dipotassium phthalocyanine, nickel phthalocyanine, poly (copper phthalocyanine), indium phthalocyanine, perfluorozinc phthalocyanine, iron chlorophthalocyanine, 2, 3-naphthalocyanine cobalt, gallium chlorophthalocyanine, oxytitanium phthalocyanine, copper perfluorophthalocyanine, manganese chlorophthalocyanine, 2, 3-naphthalocyanine tin, polychlorinated copper phthalocyanine, silver phthalocyanine, gallium phthalocyanine, copper chlorophthalocyanine, copper naphthalocyanine, copper anthracene phthalocyanine, doped copper phthalocyanine;
in the silicon-based negative electrode material, the mass percentage of the shell layer is 0.01-2%.
2. The silicon-based anode material as claimed in claim 1, wherein the phthalocyanine-based compound is a metal phthalocyanine-based compound.
3. The silicon-based anode material of claim 2, wherein the metal peptoide cyanine compound is selected from at least one of copper phthalocyanine, zinc phthalocyanine, poly (copper phthalocyanine), indium phthalocyanine, gallium phthalocyanine, perfluoro zinc phthalocyanine, perfluoro copper phthalocyanine, polychlorinated copper phthalocyanine, silver phthalocyanine, chlorinated copper phthalocyanine, naphthalene copper phthalocyanine, anthracene copper phthalocyanine, and doped copper phthalocyanine.
4. The silicon-based anode material as claimed in claim 1, wherein the silicon-based core is a carbon-silicon composite material.
5. The silicon-based anode material of claim 1, wherein the silicon-based core is silicon or an oxide of silicon.
6. The silicon-based anode material according to any one of claims 1, 4 and 5, wherein the silicon-based core has an average size of 5nm to 10 μm.
7. A silicon-based anode comprising the silicon-based anode material according to any one of claims 1 to 6.
8. A lithium battery, wherein the negative electrode of the lithium battery is the silicon-based negative electrode of claim 7.
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