CN114335477A - Silicon-based material and battery containing same - Google Patents
Silicon-based material and battery containing same Download PDFInfo
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- CN114335477A CN114335477A CN202111669963.7A CN202111669963A CN114335477A CN 114335477 A CN114335477 A CN 114335477A CN 202111669963 A CN202111669963 A CN 202111669963A CN 114335477 A CN114335477 A CN 114335477A
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- silicon
- based material
- lithium salt
- lithium
- negative electrode
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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 40
- 239000011258 core-shell 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 56
- 229910052744 lithium Inorganic materials 0.000 claims description 28
- 239000000377 silicon dioxide Substances 0.000 claims description 23
- 239000007773 negative electrode material Substances 0.000 claims description 21
- 159000000002 lithium salts Chemical class 0.000 claims description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 10
- 239000011257 shell material Substances 0.000 claims description 9
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 6
- 229910014276 N-Li Inorganic materials 0.000 claims description 4
- 229910014326 N—Li Inorganic materials 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000011162 core material Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 230000001788 irregular Effects 0.000 claims description 3
- 229910003870 O—Li Inorganic materials 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims 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 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
- 229910021389 graphene Inorganic materials 0.000 abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 6
- 238000000605 extraction Methods 0.000 abstract description 3
- 238000003780 insertion Methods 0.000 abstract description 3
- 230000037431 insertion Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 229910002804 graphite Inorganic materials 0.000 description 11
- 239000010439 graphite Substances 0.000 description 11
- 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
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 239000011267 electrode slurry Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture 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
- 230000000996 additive effect Effects 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000002994 raw material 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
- 238000001694 spray drying Methods 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
- 239000002131 composite material Substances 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 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
- 238000012512 characterization method Methods 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007788 liquid Substances 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
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 125000005463 sulfonylimide group Chemical group 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
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 244000050510 Cunninghamia lanceolata Species 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) 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
- YCOASTWZYJGKEK-UHFFFAOYSA-N [Co].[Ni].[W] Chemical compound [Co].[Ni].[W] YCOASTWZYJGKEK-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
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000006256 anode slurry Substances 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black 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
- 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
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 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
- 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
- 230000037427 ion transport Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 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
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 150000003839 salts Chemical group 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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
Abstract
The invention discloses a silicon-based material and a battery containing the same. According to the lithium salt modified graphene coated silicon-based material, the lithium salt modified graphene is coated on the surface of the silicon-based material to form the core-shell structure, and the lithium salt modified graphene is coated on the surface of the silicon material, so that the volume stress generated in the process of lithium ion insertion/extraction of the silicon material can be effectively relieved. Meanwhile, the graphene can also improve the conductivity of the electrode in a synergistic manner, so that the electrochemical properties of the battery, such as the cycle performance, the specific capacity, the charge and discharge efficiency and the like, 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 same, and particularly relates to a modified graphene-coated silicon-based material, a preparation method thereof, a negative plate containing the material and a battery.
Background
Lithium ion batteries have been widely used because of their high energy density, long cycle life, and environmental friendliness. At present, graphite is used as the most commonly used negative electrode material in lithium ion batteries, the theoretical specific capacity of the graphite is only 372mAh/g, so that the development of the lithium ion batteries to higher energy density is limited, the theoretical specific capacity of silicon materials can reach 4200mAh/g, the actual specific capacity of the silicon materials is more than 3000mAh/g, and when the graphite is replaced by the graphite as the negative electrode material of the lithium ion batteries, the energy density of the lithium ion batteries can be remarkably improved, so that the graphite becomes the next generation negative electrode active material of the lithium ion batteries with great application prospect.
However, silicon is a semiconductor material, and its conductivity is low, which is very unfavorable for rapid charging and discharging of the battery. In addition, the silicon material can generate huge volume change in the process of lithium intercalation and deintercalation, so that the SEI film on the surface of the negative electrode material is continuously cracked, regrown, cracked and regrown, and the lithium ion battery taking the silicon material as the negative electrode material has low first charge and discharge efficiency and poor cycle performance. Therefore, how to improve the conductivity of the silicon negative electrode material and reduce the volume expansion of the silicon negative electrode material during charging and discharging so as to improve the first charging and discharging efficiency and the cycle life of the lithium ion battery becomes 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, a method for preparing the same, and a negative electrode sheet and a battery including the same, the battery including the same having significantly improved rate performance.
The purpose of the invention is realized by the following technical scheme:
the silicon-based material is provided with 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.
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 invention, the thickness of the shell material in the silicon-based material is less than or equal to 10nm, such as 1-8 nm, for example 1nm, 2nm, 5nm, 8 nm.
According to the invention, the shell material with the thickness in the range is selected, so that the electronic conductivity of the silicon-based material can be better improved, the volume stress generated by the silicon-based material in the lithium ion intercalation/deintercalation process can be effectively relieved, and the volume expansion rate of the silicon-based material is 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 insertion and extraction of lithium ions are hindered, and the infiltration of electrolyte is not facilitated.
According to the invention, the silicon-based material has a particle size of 6nm to 20 μm, illustratively 6nm, 10nm, 50nm, 100nm, 500nm, 1 μm, 5 μm, 10 μm, 20 μm.
According to the invention, the silicon-based material comprises 89-99.95% by mass of silicon-based material, illustratively 94%, 95%, 96%, 97%, 98%, 99%, 99.95%.
According to the invention, the mass percentage of the lithium salt modified graphene in the silicon-based material is 0.05-11%, illustratively 0.05%, 1%, 2%, 3%, 4%, 5%, 6%.
According to the invention, the lithium salt in the lithium salt modified graphene is an organic lithium salt. Illustratively, the lithium salt is a salt containing NH2An organic lithium salt of the group. For example, the lithium salt has the structure shown in formula I:
R2-R1-NH2formula I
In the formula I, R1Is C1-7Alkylene or arylene of, R2Is lithium sulfonate or lithium sulfonimide.
Illustratively, the R is2One selected from the following groups: -S (═ 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(ii) a Wherein:
R3、R4、R5identical or different, independently of one another, from halogen or-CH substituted by one or more halogens3；
Halogen is selected from fluorine, chlorine, bromine and iodine, preferably fluorine.
According to the present invention, the lithium salt has at least one of the following structures:
wherein R is1Is C1-7Alkylene or arylene groups.
According to the invention, the lithium salt is linked to the carbon atoms of the graphene via 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 15 wt%, 20 wt%, 25 wt%, 28.2 wt%, 30 wt%, 32.1 wt% and 40 wt%.
According to the invention, the lithium salt modified graphene has a structure as shown in formula II:
in the formula II, R1And R2The definition of (1) is as before.
According to the present invention, the silicon-based material is selected from at least one of silicon monoxide, nano-silicon, silicon carbide, silicon oxide and silicon dioxide. Preferably, it is a silicon oxide.
Based on the fact that the particle size and shape of the silicon-based material also have an influence on the performance of the battery, the present application further studies the particle size and shape of the silicon-based material and provides the following scheme.
According to the invention, the silicon-based material has an average particle diameter D50 of 5nm to 20 μm, exemplary 5nm, 10nm, 50nm, 100nm, 500nm, 1 μm, 5 μm, 10 μm, 20 μm.
According to the present invention, the shape of the silicon-based material is at least one of regular or irregular granular, sheet, wire, rod, hollow sphere, tube, porous granular.
The invention also provides a negative plate which comprises a negative active material, wherein the negative 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 selected from at least one of natural graphite, artificial graphite, mesocarbon fiber, mesocarbon microbeads, soft carbon, silicon carbon and silicon-doped graphite.
According to the invention, the mass ratio of the silicon-based material to the carbon negative electrode material is not particularly defined, and is, for example, (5: 95) - (95-5), illustratively 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 includes a current collector and a negative electrode active material layer disposed 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-optical-surface copper foil, a double-optical-surface copper foil or a porous copper foil.
According to the present invention, the negative electrode active material layer may further include an additive and/or a binder.
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 Nanotube (CNT), graphene oxide, and 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 a copolymerized derivative thereof.
The invention also provides a battery, which comprises the silicon-based material or the negative plate.
The invention has the advantages of
Graphene is an ideal energy storage material due to its extremely high electron flow 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 insertion/extraction 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 electrochemical properties of the battery, such as the cycle performance, the specific capacity, the charge and discharge efficiency and the like, are improved. However, the lithium ion transmission performance of the surface of the material is reduced to a certain extent by coating the graphene, and the negative influence of the coating layer on the silicon-based material can be reduced by improving the transmission rate of lithium ions by modifying the graphene with lithium salt. Based on the organic lithium salt-modified graphene-coated silicon-based material and the 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 simultaneously, the volume stress generated by the silicon-based material in the lithium ion intercalation/deintercalation process 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 the lithium salt modified graphene-coated silicon-based material can effectively assist the migration of lithium ions in the shell layer, the ionic conductivity of the lithium ions on the surface of a negative electrode is improved, and the rate capability of a battery is further 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 taking a silicon-based material and lithium salt modified graphene oxide as raw materials to react to prepare the silicon-based material coated by the lithium salt modified graphene oxide, and then carrying out hydrothermal reduction reaction to prepare the silicon-based material.
According to the invention, said silicon-based material has the choice as indicated 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 choice as indicated above.
According to the invention, the number of layers of the graphene oxide is less than 5, the oxygen-containing functional group is greater than 30 wt%, and a large number of experiments show that: according to the difference between 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 less the organic lithium salt modified graphene oxide is used under the condition of the same coating thickness.
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 is exemplarily 1:3, 1:5, 1:10, 1:50, 1:100, 1:500, 1:1000, 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 and mixed to prepare a reaction mixture.
Preferably, the solvent may be water.
Preferably, the reaction mixture is prepared by mixing the raw materials in a stirring manner.
According to the invention, the hydrothermal reduction reaction is followed by a drying step. Preferably, the drying means may be spray drying. According to the present invention, the reducing agent used in the hydrothermal reduction reaction may be hydrazine hydrate.
According to the present invention, the method for preparing the silicon-based material comprises the steps of:
1) dispersing graphene oxide in water to prepare graphene oxide/dispersion liquid, adding a lithium salt to react, and then carrying out 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, strongly mechanically stirring to disperse the silicon-based material, and performing spray drying on the mixed solution to obtain a silicon-based material coated with the lithium salt modified graphene oxide;
3) adding hydrazine hydrate into the lithium salt modified graphene oxide coated silicon-based material prepared in the step 2), and carrying out 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 and easy to operate, and is suitable for large-scale production.
The invention also provides application of the silicon-based material in a battery. Preferably in the application as the battery negative electrode 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 further provides a battery, which includes the above silicon-based material, or includes the above negative electrode tab.
According to the present invention, the battery further comprises a positive electrode sheet including a positive electrode current collector and a positive electrode active material layer provided on at least one side surface of the positive electrode current collector.
According to the invention, the positive current collector is a single-optical-surface aluminum foil, a double-optical-surface aluminum foil or a porous aluminum foil.
According to the invention, the positive electrode active material layer comprises a positive electrode active material, and the positive electrode active material is lithium iron phosphate, ternary positive electrode material, lithium cobaltate, lithium nickel cobalt manganese oxide and lithium manganese oxide (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 cobalt aluminate, lithium nickel titanium magnesium oxide, lithium nickel oxide (Li)2NiO2) Spinel lithium manganate (LiMn)2O4) At least one of spinel Lithium Nickel Manganese Oxide (LNMO) and nickel cobalt tungsten material.
According to the present invention, the positive electrode active material layer may further include an additive and/or a binder.
Preferably, the additive is a conductive agent. Illustratively, the conductive agent is at least one of graphite, carbon black, acetylene black, graphene oxide, and carbon nanotubes.
Illustratively, the binder is selected from at least one of polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene and copolymerized derivatives thereof
The invention also provides a preparation method of the battery, which comprises the steps of preparing the silicon-based material to obtain a negative plate, and matching with a positive plate, a diaphragm and electrolyte to obtain the battery.
The preparation process of the battery is not particularly limited, and the battery can be prepared by a person skilled in the art according to the conventional process in the art.
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
Preparing an organic lithium salt modified graphene-coated silicon-based material:
(1) 3g of graphene oxide is dispersed in 1L of water, and ultrasonic dispersion is carried out to prepare graphene oxide/water dispersion liquid with the concentration of 3 mg/mL. 6g of 3-aminopropane sulfonyl imide lithium (the preparation method is referred to as synthesis and characterization of novel lithium sulfonyl imide salt and research on application of the lithium sulfonyl imide lithium salt to a lithium metal secondary battery) — is added into the graphene oxide/water dispersion, and stirred and refluxed for 12 hours at 95 ℃. Performing suction filtration, and then dispersing in water to obtain a 3-aminopropane sulfonyl imide lithium oxide modified graphene oxide/water dispersion (marked as LiGO/water dispersion, wherein the content of 3-aminopropane sulfonyl imide lithium in the LiGO is 28.2 wt% (obtained by TGA and gas chromatography) with the concentration of 1.5 mg/mL;
(2) adding to 1L of the above LiGO/water dispersion prepared in step (1)0.9985kg of silica (D) was added508 microns and irregular particles in shape), stirring for 4 hours, uniformly mixing, and spray drying the uniformly mixed solution to obtain the LiGO-coated silica;
(3) and redispersing 1kg of the LiGO-coated silicon oxide in 500mL of water, adding 1g of hydrazine hydrate, uniformly mixing, pouring into a high-temperature reaction kettle, reacting at 150 ℃ for 2h, taking out, and drying to obtain the 3-aminopropane lithium sulfoximine modified graphene-coated silicon oxide (named as LiGNs @ SiO-1).
Preparing a negative plate:
and (2) fully and uniformly mixing the LiGNs @ SiO-1 silicon-based negative electrode/graphite composite negative electrode material (the mass ratio of LiGNs @ SiO-1 to graphite is 1:1) serving as a negative electrode active substance, SBR serving as a binder, sodium carboxymethylcellulose, conductive carbon black and carbon nano tubes in deionized water to prepare negative electrode slurry, wherein the negative electrode slurry comprises 94 wt% of the LiGNs @ SiO-1/graphite composite negative electrode material, 2.5 wt% of the prepared binder with high ionic conductivity, 0.5 wt% of sodium carboxymethylcellulose, 2 wt% of conductive carbon black and 1 wt% of conductive agent carbon nano tubes, the solid content of the negative electrode slurry is 45 wt%, and the viscosity of the negative electrode slurry is 4500-. The negative electrode slurry is evenly coated on two sides of a copper foil after passing through a gauze with 150 meshes, dried for 4 hours at the temperature of 80-90 ℃, and compacted by a roller press with the compaction density of 1.5-1.7g/cm3And obtaining the negative pole piece.
Preparing a positive plate:
97 parts by mass of lithium cobaltate (4.4V lithium cobaltate from Hu south China 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 slurry is coated on the surface of an aluminum foil with the thickness of 10 mu m, the aluminum foil is dried at the temperature of 120 ℃ and rolled under the pressure of 40 tons, and the compaction density is 3.0-4.2 g/cm3And obtaining the positive plate.
Preparing a battery:
the preparation method of the battery comprises the following steps: the negative plate is matched with a positive plate, a Polyethylene (PE) porous diaphragm (PP/PE/PP composite membrane with the thickness of 9 mu m and the porosity of 41%) and electrolyte (LBC 445B33 type electrolyte of Shenzhen New Zealand science and technology Limited) to prepare the battery.
Example 2
The procedure was the same as in example 1, except that: the LiGO is prepared by reacting graphene oxide with lithium tauryl imide (the preparation method is shown in synthesis and characterization of novel lithium sulfonyl imide salts and research on application of the lithium sulfonyl imide salts to lithium metal secondary batteries) ((the content of the lithium tauryl imide in the LiGO is 32.1 wt% (obtained by TGA and gas chromatography combined test).
Example 3
The procedure was the same as in example 1, except that: the LiGO is prepared by oxidizing graphene and lithium 3-aminopropane sulfonate (by reacting 3-aminopropane sulfonate with LiOH or Li)2CO3Obtained by reaction) was prepared after the reaction, the content of lithium 3-aminopropane sulfonate in the LiGO was 39.2 wt% (obtained by TGA and gas chromatography combined test).
Example 4
The procedure was the same as in example 1, except that: the LiGO is prepared by reacting graphene oxide with lithium taurate (obtained by reacting taurine with lithium hydroxide or lithium carbonate), and the content of the lithium taurate in the LiGO is 35.2 wt% (obtained by TGA and gas chromatography combined test).
Example 5
The procedure was the same as in example 1, except that: the D50 of the silica is 0.1 μm, and during the coating process in the step (2), the amount of the LiGO is 53.3g of the LiGO which is dispersed into 2L of water, 946.7g of the silica is added, and the mixture is fully mixed and then is spray-dried. And reducing the silicon monoxide coated with the LiGO by 53g of hydrazine hydrate to obtain the LiGNs @ SiO-5.
Example 6
The procedure was the same as in example 1, except that: the D50 of the silica is 0.3 mu m, and during the coating process in the step (2), the using amount of the LiGO is 18.4g, the LiGO is dispersed into 2L of water, 981.6g of silica is added, and the mixture is fully mixed and then is spray-dried. The LiGO coated silica was then reduced with 18.4g of hydrazine hydrate.
Example 7
The procedure was the same as in example 1, except that: the D50 of the silica is 1 μm, and in the coating process in the step (2), the using amount of the LiGO is 5.6g, the LiGO is dispersed into 2L of water, 994.4g of the silica is added, and the mixture is fully mixed and then is spray-dried. The LiGO coated silica was then reduced with 5.6g hydrazine hydrate.
Example 8
The procedure was the same as in example 1, except that: the D50 of the silica is 5 μm, and during the coating process in the step (2), the using amount of the LiGO is 1.1g of the LiGO which is dispersed in 1L of water, then 998.9g of the silica is added, and the mixture is fully mixed and then is spray-dried. The LiGO coated silica was then reduced with 1.1g hydrazine hydrate.
Example 9
The preparation process was the same as example 1 except that D50 of silica was 5 μm, and the amount of LiGO used during the coating in step (2) was 2.2g of LiGO dispersed in 1L of water, followed by addition of 997.8g of silica, followed by thorough mixing and spray drying. The LiGO coated silica was then reduced with 2.2g hydrazine hydrate.
Example 10
The procedure was the same as in example 1, except that: the D50 of the silicon oxide is 5 mu m, and in the coating process in the step (2), the using amount of the LiGO is 5.5g, the LiGO is dispersed into 1L of water, and then 994.5g of the silicon oxide is added, fully mixed and spray-dried. The LiGO coated silica was then reduced with 5.5g hydrazine hydrate.
Comparative example 1
The preparation process is different from that of 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 994.5g of silica was added, mixed thoroughly and spray dried. The GO coated silica was then reduced with 5.5g hydrazine hydrate.
Comparative example 2
Compared with the embodiment 1, the difference is that: the D50 of the silicon oxide is 5 μm, and in the coating process of the step (2), 5.5g of graphene oxide is dispersed in 1L of water, then 994.5g of silicon oxide is added, and the mixture is fully mixed and then spray-dried to obtain the graphene oxide-coated silicon oxide.
Comparative example 3
Compared with the embodiment 1, the difference is that: the silica had a D50 of 5 μm and was not treated.
The test results of the examples and comparative examples 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 base material x the design thickness x the density of the coating material is the mass of the coating material, and the specific surface area of the base material is greatly influenced by the shape and the particle diameter of the material, which can be obtained by the specific surface area analyzer test. And (4) carrying out material proportioning according to the designed thickness to obtain the coating material with similar thickness.
As can be seen from the table: under the condition of the same coating thickness and silicon-based materials (examples 1-4), the performance detection results (examples 1-4, the coating thickness is designed to be about 2 nm) of batteries prepared from the LiGO-coated silicon-based materials prepared from different lithium salt modified graphene oxides are different, wherein the silicon-based materials coated with the 3-aminopropane sulfonyl imide lithium oxide modified graphene oxide have better performance; under the condition of similar coating thickness (the design coating thickness is about 1nm, and the examples 5-8), the performance of the coated silicon-based material is influenced by the excessively large or excessively small particle size of the silicon-based material; under the same particle size and the same LiGO of the silicon-based material, when the coating thickness is increased (the coating thickness is designed to be 2nm in example 9 and 5nm in example 10), the performance of the silicon-based material is also reduced; compared with the silicon-based material coated by the LiGO, the performance of the directly reduced GNs (comparative example 1, the coating thickness is designed to be 5nm) coated silicon material is improved but still lower than that of the silicon-based material (comparative example 3) which is not coated; in addition, the performance of the cell made from GO directly coated with a silicon based material (comparative example 2) was even worse than that of the cell made from uncoated silicon material (comparative example 3), mainly due to the poor electrical conductivity of GO and the inability of GO to conduct lithium ions, thus significantly increasing the impedance and ion transport of the material.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
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.
2. The silicon-based material of claim 1, wherein the lithium salt in the lithium salt-modified graphene is NH-containing2An organic lithium salt of a group, said lithium salt having the structure of formula I:
R2-R1-NH2formula I
In the formula I, R1Is C1-7Alkylene or arylene of, R2Is lithium sulfonate or lithium sulfonimide.
3. The silicon-based material of claim 2, wherein R is2One selected from the following groups: -S (═ 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(ii) a Wherein:
R3、R4、R5identical or different, independently of one another, from halogen or-CH substituted by one or more halogens3。
4. The silicon-based material of claim 2, wherein the lithium salt has at least one of the following structures:
wherein R is1Is C1-7Alkylene or arylene groups.
5. The silicon-based material of any one of claims 1-4, wherein the lithium salt is present in the lithium salt-modified graphene in an amount of 15-40 wt%.
6. A silicon-based material according to any one of claims 1 to 4, wherein the silicon-based material is selected from at least one of the group consisting of silicon monoxide, 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 granular shape, sheet shape, linear shape, rod shape, hollow spherical shape, tubular shape and porous granular shape.
7. The silicon-based material according to any one of claims 1 to 4, wherein the silicon-based material is contained in an amount of 89 to 99.95% by mass, and the lithium salt-modified graphene is contained in an amount of 0.05 to 11% by mass.
8. A negative electrode sheet comprising a negative electrode active material comprising the silicon-based material according to any one of claims 1 to 7.
9. The negative electrode sheet of claim 8, wherein the negative active material further comprises a carbon negative electrode material.
10. A battery comprising the silicon-based material according to any one of claims 1 to 7, or comprising the negative electrode sheet according to claim 8 or 9.
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