CN114335477B - Silicon-based material and battery containing same - Google Patents
Silicon-based material and battery containing same Download PDFInfo
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- CN114335477B CN114335477B CN202111669963.7A CN202111669963A CN114335477B CN 114335477 B CN114335477 B CN 114335477B CN 202111669963 A CN202111669963 A CN 202111669963A CN 114335477 B CN114335477 B CN 114335477B
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- 239000002210 silicon-based material Substances 0.000 title claims abstract description 90
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 44
- -1 lithium salt modified graphene Chemical class 0.000 claims abstract description 37
- 239000011257 shell material Substances 0.000 claims abstract description 12
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- 239000011162 core material Substances 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 59
- 229910052744 lithium Inorganic materials 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 19
- 159000000002 lithium salts Chemical class 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 13
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 13
- 239000007773 negative electrode material Substances 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 230000001788 irregular Effects 0.000 claims description 3
- 229910003870 O—Li Inorganic materials 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 27
- 239000011248 coating agent Substances 0.000 abstract description 25
- 229910021389 graphene Inorganic materials 0.000 abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 10
- 238000009830 intercalation Methods 0.000 abstract description 6
- 230000002687 intercalation Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000009831 deintercalation Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000000463 material Substances 0.000 description 13
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000010405 anode material Substances 0.000 description 9
- 238000001694 spray drying Methods 0.000 description 9
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- 230000000052 comparative effect Effects 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
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- 239000007774 positive electrode material Substances 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
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- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
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- 238000001035 drying Methods 0.000 description 3
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- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229910014276 N-Li Inorganic materials 0.000 description 2
- 229910014326 N—Li Inorganic materials 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- MCDIVJNNCHBPPS-UHFFFAOYSA-M lithium 3-aminopropane-1-sulfonate Chemical compound NCCCS(=O)(=O)[O-].[Li+] MCDIVJNNCHBPPS-UHFFFAOYSA-M 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
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- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229940104261 taurate Drugs 0.000 description 2
- SNKZJIOFVMKAOJ-UHFFFAOYSA-N 3-Aminopropanesulfonate Chemical compound NCCCS(O)(=O)=O SNKZJIOFVMKAOJ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- YCOASTWZYJGKEK-UHFFFAOYSA-N [Co].[Ni].[W] Chemical compound [Co].[Ni].[W] YCOASTWZYJGKEK-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- AXFSFUOLKZDPGI-UHFFFAOYSA-N [Li].CCCN Chemical compound [Li].CCCN AXFSFUOLKZDPGI-UHFFFAOYSA-N 0.000 description 1
- NKLLZZNEDKQOOB-UHFFFAOYSA-N [O-2].[Mg+2].[Ti+4].[Ni+2].[Li+] Chemical compound [O-2].[Mg+2].[Ti+4].[Ni+2].[Li+] NKLLZZNEDKQOOB-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 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
- 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
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
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Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a silicon-based material and a battery containing the same, wherein the silicon-based material is provided with a core-shell structure, the core-shell structure comprises a core material and a shell material, the core material comprises the silicon-based material, and the shell material comprises lithium salt modified graphene. According to the invention, the lithium salt modified graphene is coated on the surface of the silicon-based material to form the core-shell structure, and the volume stress of the silicon material in the lithium ion intercalation/deintercalation process can be effectively relieved by coating the lithium salt modified graphene on the surface of the silicon material. Meanwhile, graphene can also synergistically improve the conductivity of the electrode, so that the cycle performance, specific capacity, charge and discharge efficiency and other electrochemical performances of the battery are improved.
Description
Technical Field
The invention belongs to the technical field of batteries, relates to a silicon-based material and a battery containing the material, and particularly relates to a modified graphene coated silicon-based material, a preparation method thereof, and a negative plate and a battery containing the material.
Background
The lithium ion battery has been widely used because of its advantages of high energy density, long cycle life, environmental friendliness, and the like. At present, graphite is used as a most commonly used negative electrode material in a lithium ion battery, the theoretical specific capacity of the graphite is only 372mAh/g, so that the development of the lithium ion battery to higher energy density is limited, the theoretical specific capacity of a silicon material can reach 4200mAh/g, the actual specific capacity of the silicon material is larger than 3000mAh/g, and when the graphite is used as the negative electrode material of the lithium ion battery instead of graphite, the energy density of the lithium ion battery can be remarkably improved, and the lithium ion battery becomes a next-generation negative electrode active material of the lithium ion battery with great application prospect.
Silicon is a semiconductor material, however, which has low conductivity and thus is very disadvantageous for rapid charge and discharge of the battery. In addition, the silicon material can generate huge volume change in the process of lithium intercalation, so that SEI film on the surface of the anode material is continuously cracked, regrown, cracked and regrown, thereby leading to low first charge and discharge efficiency and poor cycle performance of the lithium ion battery taking the silicon material as the anode material. Therefore, how to improve the conductivity of the silicon anode material and reduce the volume expansion of the silicon anode material during charging and discharging, so as to improve the first charging and discharging efficiency and the cycle life of the lithium ion battery is a technical problem to be solved in the field.
Disclosure of Invention
In order to improve the above technical problems, the present invention provides a silicon-based material having improved electron conductivity, reduced volume expansion rate, and improved cycle life, and a battery including the same, which has significantly improved rate capability, a method of preparing the same, and a negative electrode sheet and a battery including the same.
The invention aims at realizing the following technical scheme:
a silicon-based material having a core-shell structure comprising a core material and a shell material, wherein the core material comprises a silicon-based material and the shell material comprises lithium salt modified graphene.
According to the invention, the lithium salt modified graphene is coated on the surface of a silicon-based material to form the core-shell structure.
According to the present invention, in the silicon-based material, the thickness of the shell material is 10nm or less, for example, 1 to 8nm, and exemplary 1nm, 2nm, 5nm, 8nm.
According to the invention, the shell material with the thickness range is selected, so that the electronic conductivity of the silicon-based material can be better improved, the volume stress generated in the lithium ion intercalation/deintercalation process of the silicon-based material can be effectively relieved, and the volume expansion rate of the silicon-based material can be further reduced. A large number of experimental studies have found that: if the thickness of the shell material is greater than or equal to 10nm, the intercalation and deintercalation of lithium ions are hindered, and the infiltration of electrolyte is also unfavorable.
According to the present invention, the particle size of the silicon-based material is 6nm to 20. Mu.m, and exemplary is 6nm, 10nm, 50nm, 100nm, 500nm, 1. Mu.m, 5. Mu.m, 10. Mu.m, 20. Mu.m.
According to the invention, the mass percentage of the silicon-based material is 89% -99.95%, and the mass percentage is 94%, 95%, 96%, 97%, 98%, 99% and 99.95% in the silicon-based material.
According to the invention, in the silicon-based material, the mass percentage of the lithium salt modified graphene is 0.05% -11%, and the mass percentage is 0.05%, 1%, 2%, 3%, 4%, 5% and 6% in an exemplary way.
According to the invention, the lithium salt in the lithium salt modified graphene is an organic lithium salt. Illustratively, the lithium salt is an organolithium salt containing an NH 2 group. For example, the lithium salt has a structure represented by formula I:
r 2-R1-NH2 formula I
In formula I, R 1 is alkylene or arylene of C 1-7 and R 2 is lithium sulfonate or lithium sulfonimide.
Illustratively, the R 2 is selected from one ：-S(＝O)(＝O)-O-Li+、-S(＝O)(＝O)-N-Li+-S(＝O)(＝O)-R3、-S(＝O)(＝O)-N-Li+-S(＝O)(＝N)-R4-S(＝O)(＝O)-R5; of the following groups:
R 3、R4、R5, identical or different, are independently of one another selected from halogen or-CH 3 substituted by one or more halogens;
Halogen is selected from fluorine, chlorine, bromine and iodine, preferably fluorine.
According to the invention, the lithium salt has at least one of the following structures:
Wherein R 1 is an alkylene or arylene group of C 1-7.
According to the invention, the lithium salt is linked to a carbon atom on graphene through an-NH-group.
According to the invention, the weight ratio of the lithium salt in the lithium salt modified graphene is 15-40 wt%, and is exemplified by 15wt%, 20wt%, 25wt%, 28.2wt%, 30wt%, 32.1wt%, 40wt%.
According to the present invention, the lithium salt modified graphene has a structure as shown in formula II:
In formula II, R 1 and R 2 are as defined above.
According to the present invention, the silicon-based material is selected from at least one of silicon oxide, nano silicon, silicon carbide, silicon oxide, and silicon dioxide. Preferably silicon oxide.
It was found that the particle size and shape of the silicon-based material also have an effect on the performance of the battery, and based on this, the present application further studied the particle size and shape of the silicon-based material and provided the following.
According to the present invention, the average particle diameter D50 of the silicon-based material is 5nm to 20. Mu.m, and exemplary is 5nm, 10nm, 50nm, 100nm, 500nm, 1. Mu.m, 5. Mu.m, 10. Mu.m, 20. Mu.m.
According to the present invention, the silicon-based material has at least one of regular or irregular granular, plate-like, wire-like, rod-like, hollow sphere-like, tubular, and porous granular shape.
The invention also provides a negative electrode plate, which comprises a negative electrode active material, wherein the negative electrode active material comprises the silicon-based material.
According to the present invention, the anode active material further includes a carbon anode material.
According to the invention, the carbon negative electrode material is at least one selected from natural graphite, artificial graphite, mesophase carbon fiber, mesophase carbon microsphere, soft carbon, silicon carbon and silicon-doped graphite.
According to the invention, the mass ratio of the silicon-based material and the carbon anode material is not particularly defined, for example, is (5-95): (95-5), and exemplary is 5:95, 10:90, 15:85, 20:80, 25:75, 30:70, 40:60, 50:50, 60:40, 70:30, 75:25, 80:20, 85:15, 90:10 or 95:5.
According to the present invention, the negative electrode sheet further comprises a current collector and a negative electrode active material layer provided on at least one side surface of the current collector, the negative electrode active material layer including the negative electrode active material therein.
According to the invention, the current collector is a single-sided copper foil, a double-sided copper foil or a porous copper foil.
According to the present invention, an additive and/or a binder may be further included in the anode active material layer.
Preferably, the additive is at least one of a conductive agent and a dispersant.
Illustratively, the conductive agent is at least one of conductive carbon black (SP), ketjen black, conductive fiber, conductive polymer, acetylene black, carbon Nanotubes (CNT), graphene oxide, and crystalline flake graphite.
Illustratively, the dispersant is sodium carboxymethyl cellulose or lithium carboxymethyl cellulose.
Illustratively, the binder is selected from at least one of polyacrylic acid, polyacrylate, styrene-butadiene rubber (SBR), and co-polymerized derivatives thereof.
The invention also provides a battery, which comprises the silicon-based material or the negative plate.
The beneficial effects of the invention are that
Graphene is an ideal energy storage material with extremely high electron current carrying rate, high electrical conductivity, high thermal conductivity, high mechanical strength and large specific surface area. The graphene is coated on the surface of the silicon material, so that the volume stress generated in the process of lithium ion intercalation/deintercalation of the silicon material can be effectively relieved. The addition of the graphene can also synergistically improve the conductivity of the electrode, so that the cycle performance, specific capacity, charge and discharge efficiency and other electrochemical performances of the battery are improved. However, the coating of the graphene can reduce the lithium ion transmission performance of the surface of the material to a certain extent, and the lithium salt modification of the graphene can improve the lithium ion transmission rate and reduce the negative influence of the coating layer on the silicon-based material. Based on the material, the invention provides an organolithium salt modified graphene coated silicon-based material and a preparation method thereof. Specifically, the lithium salt modified graphene coated silicon-based material has the following advantages:
(1) According to the invention, the graphene with excellent flexibility is coated on the surface of the silicon-based material, so that on one hand, the electronic conductivity of the silicon-based material can be improved, and meanwhile, the volume stress generated in the lithium ion intercalation/deintercalation process of the silicon-based material can be effectively relieved, so that the volume expansion rate of the silicon-based material is reduced, and the cycle life is prolonged.
(2) The shell layer of the lithium salt modified graphene coated silicon-based material has organic lithium, so that migration of lithium ions on the shell layer can be effectively assisted, ion conductivity of the lithium ions on the surface of a negative electrode can be improved, and rate performance of a battery can be improved.
Detailed Description
The invention also provides a preparation method of the silicon-based material, which comprises the following steps: the preparation method comprises the steps of reacting a silicon-based material with lithium salt modified graphene oxide as a raw material to prepare the silicon-based material coated with the lithium salt modified graphene oxide, and then performing hydrothermal reduction reaction to prepare the silicon-based material.
According to the invention, the silicon-based material has the options as shown above.
According to the invention, the lithium salt modified graphene oxide raw material is obtained by modifying graphene oxide with lithium salt.
According to the invention, the lithium salt has the options as indicated above.
According to the invention, the number of layers of the graphene oxide is <5 layers, the oxygen-containing functional group is >30wt%, and a large number of experiments surprisingly find that: according to the difference of the particle size and the coating thickness of the silicon-based material, when the particle size of the silicon-based material is increased, the specific surface area is reduced, so that the dosage of the organic lithium salt modified graphene oxide required under the same coating thickness condition is smaller.
According to the invention, the mass ratio of the lithium salt modified graphene oxide to the silicon-based material is 5:10000-1:8, preferably 1:2000-1:5, more preferably 1:1000-1:10, and exemplary are 1:3, 1:5, 1:10, 1:50, 1:100, 1:500, 1:1000, and 1:2000.
According to the invention, the reaction is carried out in the presence of a solvent. For example, the lithium salt modified graphene oxide is dispersed in a solvent, and then a silicon-based material is added for mixing to prepare a reaction mixture.
Preferably, the solvent may be water.
Preferably, the reaction mixture is prepared by stirring the raw materials.
According to the invention, the hydrothermal reduction reaction is followed by a drying step. Preferably, the drying mode may be spray drying. According to the invention, the reducing agent used in the hydrothermal reduction reaction may be hydrazine hydrate.
According to the invention, the preparation method of the silicon-based material comprises the following steps:
1) Dispersing graphene oxide in water to prepare graphene oxide/dispersion liquid, adding lithium salt for reaction, and performing suction filtration to obtain lithium salt modified graphene oxide;
2) Re-dispersing the lithium salt modified graphene oxide obtained in the step 1) in water, then adding a granular silicon-based material, performing ultrasonic treatment, performing strong mechanical stirring to disperse the silicon-based material, and performing spray drying on the mixed solution to obtain a lithium salt modified graphene oxide coated silicon-based material;
3) And (3) adding hydrazine hydrate into the lithium salt modified graphene oxide coated silicon-based material prepared in the step (2) and performing hydrothermal reduction reaction to obtain the modified lithium salt modified graphene coated silicon-based material.
In conclusion, the preparation method of the silicon-based material provided by the invention is simple, easy to operate and suitable for large-scale production.
The invention also provides application of the silicon-based material in a battery. Preferably in use as a battery anode material.
The invention also provides a preparation method of the negative plate, which comprises the step of coating the slurry containing the silicon-based material on a current collector to prepare the negative plate.
As described above, the present invention also provides a battery including the above silicon-based material, or including the above negative electrode sheet.
According to the present invention, the battery further includes a positive electrode sheet including a positive electrode current collector and a positive electrode active material layer disposed on at least one side surface of the positive electrode current collector.
According to the invention, the positive current collector is a single-smooth aluminum foil, a double-smooth aluminum foil or a porous aluminum foil.
According to the present invention, the positive electrode active material layer includes therein a positive electrode active material, which is at least one of lithium iron phosphate, ternary positive electrode material, lithium cobaltate, lithium nickel cobalt manganate, lithium manganate (LiMnO 2), lithium nickel cobalt aluminate, lithium nickel cobalt manganese aluminate, nickel cobalt aluminum tungsten material, lithium-rich manganese-based solid solution positive electrode material, lithium nickel cobaltate, lithium nickel titanium magnesium oxide, lithium nickelate (Li 2NiO2), spinel lithium manganate (LiMn 2O4), spinel Lithium Nickel Manganate (LNMO), and nickel cobalt tungsten material.
According to the present invention, an additive and/or a binder may be further included in the positive electrode active material layer.
Preferably, the additive is a conductive agent. Illustratively, the conductive agent is at least one of graphite, carbon black, acetylene black, graphene oxide, carbon nanotubes.
Illustratively, the binder is selected from at least one of polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene, and co-derivatives thereof
The invention also provides a preparation method of the battery, which comprises the steps of preparing the silicon-based material into a negative plate, and matching the negative plate, the diaphragm and the electrolyte to prepare the battery.
The present invention is not particularly limited to the process for preparing the battery, and one skilled in the art may perform the preparation of the battery according to the conventional process in the art.
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
Preparing an organolithium salt modified graphene coated silicon-based material:
(1) 3g of graphene oxide was dispersed in 1L of water, and the dispersion was subjected to ultrasonic dispersion to prepare a graphene oxide/aqueous dispersion having a concentration of 3 mg/mL. 6g of lithium 3-aminopropane sulphonimide (for preparation see "synthesis, characterization of novel sulphonimide lithium salts and their application to lithium metal secondary batteries," "Ma Jiang") were added to the graphene oxide/water dispersion and stirred at 95℃under reflux for 12h. Suction filtering and then dispersing in water to obtain 3-aminopropane sulfonimide lithium modified graphene oxide/water dispersion with the concentration of 1.5mg/mL (which is LiGO/water dispersion, wherein the content of 3-aminopropane sulfonimide lithium in LiGO is 28.2wt% (obtained by TGA and gas chromatography combined test));
(2) Adding 0.9985kg of silicon oxide (D 50 is 8 mu m, irregular particles in shape) into 1L of LiGO/water dispersion prepared in the step (1), stirring for 4 hours, uniformly mixing, and performing spray drying on the uniformly mixed solution to obtain LiGO coated silicon oxide;
(3) 1kg of the LiGO-coated silica is redispersed in 500mL of water, 1g of hydrazine hydrate is added, the mixture is poured into a high-temperature reaction kettle after being uniformly mixed, the mixture is reacted for 2 hours at 150 ℃, and the mixture is taken out and dried to obtain the 3-aminopropane lithium-sulfimide modified graphene-coated silica (named LiGNs@SiO-1).
Preparing a negative plate:
The anode active material, the LiGNs@SiO-1 silicon-based anode/graphite composite anode material (the mass ratio of the LiGNs@SiO-1 to the graphite is 1:1), the binder SBR, sodium carboxymethyl cellulose and conductive carbon black, and the carbon nano tube are dispersed in deionized water and fully and uniformly mixed to prepare anode slurry, wherein the anode slurry comprises 94wt% of the LiGNs@SiO-1/graphite composite anode material, 2.5wt% of the prepared high-ionic-conductivity binder, 0.5wt% of sodium carboxymethyl cellulose, 2wt% of the conductive carbon black and 1wt% of the conductive carbon nano tube, the solid content of the anode slurry is 45wt%, and the viscosity is 4500-6500 mPa.s. And (3) after passing through a 150-mesh gauze, uniformly coating the anode slurry on two sides of a copper foil, drying for 4 hours at 80-90 ℃, compacting the anode slurry by using a roller press, wherein the compaction density is 1.5-1.7g/cm 3, and obtaining the anode pole piece.
Preparation of a positive plate:
97 parts by mass of lithium cobaltate (4.4V lithium cobaltate of Hunan fir energy science and technology Co., ltd.), 1.5 parts by mass of conductive agent carbon black, 1.5 parts by mass of binder PVDF and 50 parts by mass of solvent NMP are fully and uniformly mixed to prepare lithium cobaltate anode slurry, the lithium cobaltate anode slurry is coated on the surface of 10 mu m aluminum foil, and then the lithium cobaltate anode slurry is dried at 120 ℃ and rolled under 40 tons of pressure, and the compacted density is 3.0-4.2 g/cm 3, so that the anode plate is obtained.
Preparation of the battery:
The preparation method of the battery comprises the following steps: the above-mentioned negative electrode sheet, positive electrode sheet, polyethylene (PE) porous diaphragm (PP/PE/PP composite film, thickness 9 μm, porosity 41%), electrolyte (LBC 445B33 type electrolyte from Shenzhen New Country science and technology Co., ltd.) were mixed to prepare a battery.
Example 2
The preparation process was the same as in example 1, except that: liGO was prepared by reacting graphene oxide with lithium taurinate (preparation method see "synthesis, characterization of novel lithium sulfonimide salt and its application in research on lithium metal secondary battery— Ma Jiang") (content of lithium taurinate in LiGO is 32.1wt% (obtained by TGA and gas chromatography combined test).
Example 3
The preparation process was the same as in example 1, except that: liGO is prepared by reacting graphene oxide with lithium 3-aminopropanesulfonate (obtained by reacting 3-aminopropanesulfonic acid with LiOH or Li 2CO3), wherein the content of the lithium 3-aminopropanesulfonate in LiGO is 39.2wt% (obtained by using TGA and gas chromatography).
Example 4
The preparation process was the same as in example 1, except that: liGO is prepared by reacting graphene oxide with lithium taurate (obtained by reacting taurine with lithium hydroxide or lithium carbonate), and the content of lithium taurate in LiGO is 35.2wt% (obtained by TGA and gas chromatography combined test).
Example 5
The preparation process was the same as in example 1, except that: the silica D50 was 0.1 μm and the amount LiGO was used in the coating process of step (2) by dispersing 53.3, 53.3g LiGO in 2L of water, then adding 946.7g of silica, mixing thoroughly and spray drying. And then reducing LiGO coated silica by 53g of hydrazine hydrate to obtain LiGNs@SiO-5.
Example 6
The preparation process was the same as in example 1, except that: the silica D50 was 0.3. Mu.m, and the LiGO amount was 18.4: 18.4g LiGO dispersed in 2L of water during the coating in step (2), followed by adding 981.6g of silica, thoroughly mixing and spray drying. And then reducing LiGO the coated silicon oxide by 18.4g of hydrazine hydrate.
Example 7
The preparation process was the same as in example 1, except that: the silica D50 was 1 μm, and LiGO.6: 5.6g LiGO was dispersed in 2L of water during the coating in step (2), followed by adding 994.4g of silica, thoroughly mixing and spray drying. And then reducing LiGO g of hydrazine hydrate to obtain the coated silicon oxide.
Example 8
The preparation process was the same as in example 1, except that: the silica D50 was 5. Mu.m, and LiGO was dispersed in 1L of water in an amount of 1.1: 1.1g LiGO during the coating in step (2), followed by adding 998.9g of silica, thoroughly mixing and spray drying. And then reducing LiGO the coated silicon oxide by using 1.1g of hydrazine hydrate.
Example 9
The procedure was the same as in example 1, except that the silica had a D50 of 5. Mu.m, and that the amount of LiGO was 2.2: 2.2g LiGO in the coating in step (2) dispersed in 1L of water, followed by adding 997.8g of silica, thoroughly mixing and spray drying. And then reducing LiGO the coated silicon oxide by 2.2g of hydrazine hydrate.
Example 10
The preparation process was the same as in example 1, except that: the silica D50 was 5. Mu.m, and LiGO was dispersed in 1L of water in an amount of 5.5: 5.5g LiGO during the coating in step (2), and then 994.5g of silica was added, thoroughly mixed and spray dried. And then reducing LiGO g of hydrazine hydrate to reduce LiGO g of coated silicon oxide.
Comparative example 1
The preparation process differs from example 1 in that: the silica D50 was 5 μm, and during the coating in step (2), 5.5g of GO was dispersed in 1L of water, and then 994.5g of silica was added, thoroughly mixed and spray dried. And then reducing the GO-coated silicon oxide by 5.5g of hydrazine hydrate.
Comparative example 2
The difference from example 1 is that: the D50 of the silica was 5 μm, and in the coating process of the step (2), 5.5g of graphene oxide was dispersed in 1L of water, and then 994.5g of silica was added to the mixture, followed by spray drying to obtain graphene oxide-coated silica.
Comparative example 3
The difference from example 1 is that: the D50 of the silica was 5 μm and was not subjected to any treatment.
The test results of each example and comparative example are shown in table 1 below.
TABLE 1
In the present invention, the coating thickness is designed, that is, the specific surface area of the substrate x the design thickness x the density of the coating material=the mass of the coating material, whereas the specific surface area of the substrate is greatly affected by the shape and particle size of the material, which can be obtained by testing with a specific surface area analyzer. And (5) carrying out material proportioning according to the design thickness to obtain the coating material with similar thickness.
From the table it can be seen that: under the condition of the same coating thickness and silicon-based materials (examples 1-4), the performance detection results (examples 1-4, design coating thickness about 2 nm) of the battery prepared by LiGO coating silicon-based materials prepared by different lithium salt modified graphene oxides are different, wherein the performance of the silicon-based materials coated by 3-aminopropane sulfonyl imide lithium modified graphene oxides is better; under the condition of similar coating thickness (design coating thickness is about 1nm, examples 5-8), the performance of the coated silicon-based material can be influenced by the excessively large or excessively small particle size of the silicon-based material; however, when the coating thickness is increased (the coating thickness is 2nm in example 9 and 5nm in example 10) under the same particle size and LiGO of the silicon-based material, the performance of the silicon-based material is also reduced; compared with the silicon-based material coated by LiGO, the performance of the directly reduced GNs (comparative example 1, with the designed coating thickness of 5 nm) coated silicon material is improved compared with the silicon-based material without coating treatment (comparative example 3) but still lower than that of the examples 1-10 of the invention; in addition, the performance of the cell made from GO directly coated silicon-based material (comparative example 2) is even worse than that of the uncoated silicon material (comparative example 3), mainly because GO is very poor in conductivity and is not conductive to lithium ions, thus significantly increasing the resistance and ion migration of the material.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The silicon-based material is characterized by having a core-shell structure, wherein the core-shell structure comprises a core material and a shell material, the core material comprises the silicon-based material, and the shell material comprises lithium salt modified graphene;
In the core-shell structure, the thickness of the shell material is less than or equal to 10nm;
The lithium salt in the lithium salt modified graphene is organic lithium salt containing NH 2 groups, and the lithium salt has a structure shown in a formula I: r 2-R1-NH2 formula I
In the formula I, R 1 is alkylene or arylene of C 1-7, and R 2 is lithium sulfonate or lithium sulfonyl imide;
the particle size of the silicon-based material is 6 nm-20 mu m.
2. The silicon-based material of claim 1, wherein R 2 is selected from one of the following ：-S(=O)(=O)-O-Li+、-S(=O)(=O)-N- Li+-S(=O)(=O)- R3、-S(=O)(=O)-N- Li+-S(=O)(=N)- R4-S(=O)(=O)- R5; wherein:
R 3、R4、R5, which are identical or different, are independently of one another selected from halogen or-CH 3 substituted by one or more halogens.
3. The silicon-based material of claim 1, wherein the lithium salt has at least one of the following structures:
Wherein R 1 is an alkylene or arylene group of C 1-7.
4. The silicon-based material according to any one of claims 1 to 3, wherein the weight ratio of lithium salt in the lithium salt modified graphene is 15 to 40wt%.
5. A silicon-based material according to any one of claims 1-3, wherein the silicon-based material is selected from at least one of silicon oxide, nano-silicon, silicon carbide, silicon oxide and silicon dioxide;
And/or the shape of the silicon-based material is at least one of regular or irregular particles, sheets, lines, rods, hollow spheres, tubes and porous particles.
6. A silicon-based material according to any one of claims 1 to 3, wherein the mass percentage of the silicon-based material is 89% -99.95% and the mass percentage of the lithium salt modified graphene is 0.05% -11%.
7. A negative electrode sheet, characterized in that the negative electrode sheet comprises a negative electrode active material comprising the silicon-based material according to any one of claims 1 to 6.
8. The negative electrode sheet according to claim 7, wherein the negative electrode active material further comprises a carbon negative electrode material.
9. A battery comprising the silicon-based material of any one of claims 1 to 6, or comprising the negative electrode sheet of claim 7 or 8.
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