CN117276513A - Composite negative electrode material for lithium ion battery, preparation method and lithium ion battery - Google Patents
Composite negative electrode material for lithium ion battery, preparation method and lithium ion battery Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000007773 negative electrode material Substances 0.000 title claims description 8
- 239000002243 precursor Substances 0.000 claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 41
- 239000010439 graphite Substances 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 36
- 238000000576 coating method Methods 0.000 claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012298 atmosphere Substances 0.000 claims abstract description 19
- 239000010405 anode material Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005977 Ethylene Substances 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005049 silicon tetrachloride Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 7
- 239000000463 material Substances 0.000 abstract description 17
- 239000002002 slurry Substances 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- 239000006258 conductive agent Substances 0.000 description 10
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 description 8
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 8
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 229910013870 LiPF 6 Inorganic materials 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000002174 Styrene-butadiene Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
- SFXFPRFVFALOCV-UHFFFAOYSA-N silicon;tetraethyl silicate Chemical compound [Si].CCO[Si](OCC)(OCC)OCC SFXFPRFVFALOCV-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 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
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001007 puffing effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a composite anode material for a lithium ion battery, a preparation method and the lithium ion battery. The composite anode material Si-xSiO for the lithium ion battery 2 The preparation method of the @ EG@C comprises the following steps: s1, adding water into expanded graphite, ultrasonically stirring, sequentially adding organic silicon and ethanol for a first reaction, and adjusting the pH value for a second reaction to obtain a first precursor H 2 SiO 3 EG; s2, mixing the first precursor and magnesium powder, and then calcining the mixture in an inert atmosphere to obtain a second precursor Si@EG; s3,Subjecting the second precursor to 60 Co irradiation source irradiation to obtain a third precursor Si-xSiO 2 EG; and S4, performing chemical vapor deposition on the third precursor in an ethylene atmosphere to perform carbon coating, so as to obtain the composite anode material for the lithium ion battery. The composite anode material for the lithium ion battery effectively relieves the problems of volume expansion and poor conductivity of Si materials, and the lithium ion battery prepared by using the material has good electrochemical performance.
Description
Technical Field
The invention belongs to the field of preparation of lithium ion battery cathode materials, and particularly relates to a composite cathode material for a lithium ion battery, a preparation method and the lithium ion battery.
Background
The development of electric vehicles and large-scale energy storage networks has placed higher demands on the performance (capacity, cycle, safety, etc.) of lithium ion batteries. The current commercialized graphite anode material has better first-circle coulombic efficiency and rate capability, but the specific capacity of the current commercialized graphite anode material limits the better development of the current commercialized graphite anode material. Therefore, the search for high capacity, high cycle stability anode materials is now the focus of research.
The silicon material is considered as the anode material of the lithium ion battery with the most potential because of the characteristics of the highest theoretical specific capacity, proper lithium intercalation platform, large storage capacity and the like. However, silicon materials have the following disadvantages: the material expands in larger volume during the cycle, destroying the electrode structure, resulting in a continuous decrease in discharge capacity. How to effectively improve the problems is a hot spot of research. In order to solve the above problems, the improvement is conventionally performed by adopting a carbon coating method, but the effect is limited due to the huge expansion of silicon.
Disclosure of Invention
The invention aims to provide a composite anode material for a lithium ion battery, a preparation method and the lithium ion battery, wherein nano silicon particles are inserted into an expanded graphite layer to form Si@EG, and the nano silicon particles are prepared by 60 Co irradiation source irradiation to form Si-xSiO 2 EG, then at Si-xSiO by CVD method 2 Uniformly coating the surface of the @ EG with a C layer to form Si-xSiO 2 EG@C composite material, siO is formed on the surface of Si 2 Layer reduced volume expansionThe expansion is restrained by the expanded graphite layer and the carbon coating, the structure effectively relieves the problems of volume expansion and poor conductivity of Si materials, and the lithium ion battery prepared by using the material shows good electrochemical performance.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a composite anode material for a lithium ion battery, wherein the composite material is Si-xSiO 2 Eg@c comprising the steps of:
s1, adding water into expanded graphite, ultrasonically stirring, sequentially adding organic silicon and ethanol for a first reaction, and adjusting the pH value for a second reaction to obtain a first precursor H 2 SiO 3 @EG；
S2, mixing the first precursor and magnesium powder, and then calcining the mixture in an inert atmosphere to obtain a second precursor Si@EG;
s3, carrying out the second precursor 60 Co irradiation source irradiation to obtain a third precursor Si-xSiO 2 @EG；
And S4, performing chemical vapor deposition on the third precursor in an ethylene atmosphere to perform carbon coating, so as to obtain the composite anode material for the lithium ion battery.
In the preparation method, the organic silicon can be one or more of tetraethoxysilane and silicon tetrachloride, and preferably silicon tetrachloride.
In the preparation method, the expanded graphite (Expanded Graphite, abbreviated as EG) is a loose and porous worm-like substance obtained by intercalation, washing, drying and high-temperature puffing of natural graphite flakes. Wherein the expansion coefficient of the expanded graphite is generally 100-300 times. The expanded graphite may be prepared according to methods disclosed in the literature or may be purchased commercially. In a specific embodiment of the present invention, the expanded graphite is expanded graphite manufactured by Qingdao gold Japanese graphite Co.
In the above preparation method, the molar ratio of the organosilicon to the expanded graphite may be 1: (0.1 to 20), specifically 1: (2-4), 1:4 or 1:2, preferably 1: (3 to 4), more preferably 1:4, a step of;
the mass ratio of the expanded graphite to the water can be (1-20): 100, specifically can be 12:100;
the ratio of the expanded graphite to ethanol may be 1mol: (0.2-20) mL, specifically 1mol:1mL.
The ethanol is absolute ethanol.
In the preparation method, the temperature of the reaction in the step (1) can be 40-100 ℃, specifically 80 ℃, and the time can be 2-8 h, specifically 4h;
the first reaction is carried out under the stirring condition, and the stirring speed is 500-1000 r/min, specifically 500r/min, 800r/min or 1000r/min.
In the above preparation method, the pH adjustment may be performed by adjusting the pH to 3 to 8 with ammonia, preferably to 4 to 6, such as to 5;
the temperature of the second reaction is 40-100 ℃, specifically 80 ℃, the time is 2-12 h, specifically 5h, 6h, 2h, 4h or 12h;
the second reaction is carried out under the stirring condition, and the stirring speed is 500-1000 r/min, specifically 500r/min, 800r/min or 1000r/min.
The method further comprises the steps of filtering, washing and drying sequentially after the second reaction in the step (1).
In the above preparation method, the mass ratio of the first precursor to the magnesium powder may be 1: (0.1-2), specifically 1: (0.25-1), 1:1 or 1:0.25;
the calcination treatment can be to presintered for 4-8 hours at 150-250 ℃ and then calcination for 8-24 hours at 800-1200 ℃, specifically 250 ℃ for 5 hours and then 1200 ℃ for 20 hours. Wherein, the temperature rising rate can be 1-10 ℃/min, such as 5 ℃/min.
The inert atmosphere may specifically be an argon atmosphere.
The method further comprises the steps of washing with dilute hydrochloric acid, filtering and drying after the calcination treatment.
In the above preparation method, the 60 Co spokeThe irradiation dose of the irradiation source can be 10-1000 Kgy, and can be specifically 400-600 Kgy, 500Kgy, 400Kgy or 600Kgy; the irradiation time can be 0.1-10 h, and can be specifically 1-3 h, 2h, 1h or 3h; preferably 2h at a 500Kgy dose or 3h at a 600Kgy dose.
In the above preparation method, the flow rate of the ethylene may be 0.1-1L/min, specifically may be 0.3-1L/min, 0.5L/min, 0.3L/min, 1L/min or 0.56L/min, preferably 0.5L/min, 0.56L/min;
the temperature of the chemical vapor deposition can be 600-1000 ℃, and can be 750-950 ℃, 950 ℃ and 750 ℃; the time can be 1-12 h, and can be 1-8 h, 1h, 8h and 6h; preferably at 950 ℃ for 6 hours or 8 hours.
The chemical vapor deposition is performed in a CVD furnace.
In a second aspect, the present invention provides a composite anode material for a lithium ion battery, which is prepared by the preparation method according to any one of the above aspects.
In a third aspect, the invention provides a lithium ion battery, which comprises a positive electrode plate, a negative electrode plate, a diaphragm and electrolyte, wherein the negative electrode plate comprises a current collector and the composite negative electrode material for the lithium ion battery loaded on the current collector.
In the lithium ion battery, the negative electrode plate is prepared by coating slurry formed by mixing the composite negative electrode material for the lithium ion battery, a conductive agent, an adhesive and an organic solvent on a current collector;
in an embodiment of the present invention, the conductive agent is carbon black (SP);
the binder may be carboxymethyl cellulose (CMC) and styrene butadiene rubber emulsion (SBR), and in an embodiment of the present invention, the binder has a mass ratio of 1:1.5 carboxymethylcellulose and styrene-butadiene rubber emulsion;
in an embodiment of the present invention, the mass ratio of the composite anode material for lithium ion battery, the conductive agent, and the binder is 8:1:1, a step of;
in an embodiment of the invention, the organic solvent is N-methyl dipyrrolidone;
the thickness of the slurry may be from 5 to 100 microns, such as 35 microns; in embodiments of the invention, the coating thickness is 50 to 100 microns.
The active material in the positive electrode sheet may be any one of a lithium intercalation material, a lithium alloy material, and lithium metal, such as lithium metal.
The electrolyte comprises electrolyte salt, organic solvent and additives, such as 1M LiPF 6 EC/DMC/FEC (volume ratio 1:1:0.1).
The separator is any one of polyethylene, polypropylene and related composite and modified polymer microporous membranes, such as Celgard 2400.
The invention has the following beneficial effects:
the inventors of the present invention have found, through intensive studies, that, in the material prepared by the above method, nano silicon particles are intercalated into an expanded graphite layer to form Si@EG by 60 Co irradiation source irradiation to form Si-xSiO 2 EG, then at Si-xSiO by CVD method 2 Uniformly coating the surface of the @ EG with a C layer to form Si-xSiO 2 EG@C composite material due to SiO 2 The expansion of the material is smaller than that of Si, so that the structure is more effective than that of Si@EG@C, and the problems of volume expansion and poor conductivity of the Si material are relieved, and therefore, the lithium ion battery prepared by the material shows good electrochemical performance. The negative electrode material and a positive electrode material, a diaphragm, a nonaqueous electrolyte and the like which are widely used in the lithium ion battery form a high-performance lithium ion battery, and the achievement of the invention is obtained.
Drawings
FIG. 1 Si-xSiO according to example 1 of the present invention 2 Electrical properties of eg@c composite material.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof. The examples provided below are intended as guidelines for further modifications by one of ordinary skill in the art and are not to be construed as limiting the invention in any way.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are all commercially available.
The expanded graphite in the following examples was produced by Qingdao gold japanese graphite limited under the product name of expanded graphite (worm) 9980300.
Example 1
1. Preparing a composite material:
(a) Weighing 12g (1 mol) of expanded graphite, putting the expanded graphite into a beaker, adding 100mL of water, stirring for 4 hours in an ultrasonic manner, adding organic silicon tetraethoxysilane with the expanded graphite according to a molar ratio of 1:4, adding 1mL of absolute ethyl alcohol, heating to 80 ℃, and reacting for 4 hours at a stirring rotation speed of 500 r/min; adding ammonia water to adjust the pH to 5, and continuously stirring for 5 hours; filtering, washing and drying to obtain a first precursor H 2 SiO 3 @EG；
(b) First precursor H 2 SiO 3 EG and magnesium powder according to 1: after being uniformly mixed according to the mass ratio, the mixture is placed into a porcelain boat and placed into an Ar atmosphere furnace to be presintered at 250 ℃ for 5 hours and then calcined at 1200 ℃ for 20 hours (the heating rate is 5 ℃/min), cooled, washed by dilute hydrochloric acid, filtered and dried to obtain a second precursor Si@EG;
(c) Passing the second precursor Si@EG through a dose of 500Kgy 60 After Co irradiation source irradiates for 2 hours, a third precursor Si-xSiO is obtained 2 @EG；
(d) The third precursor Si-xSiO 2 C of 0.5L/min of @ EG placed in a CVD furnace 2 H 4 Reacting for 6h at 950 ℃ in atmosphere to obtain Si-xSiO 2 Eg@c composite.
2. Preparation of a lithium ion battery:
mixing 80 parts by weight of the prepared composite material with 10 parts by weight of the conductive agent SP, 10 parts by weight of the binder CMC and SBR (mass ratio of 1:1.5), adding a proper amount of N-methyl dipyrrolidone, continuously stirring until the slurry is uniform, preparing into slurry, coating the slurry on a copper foil current collector (coating thickness is 50-100 mu m) by an automatic coating machine, and vacuum drying in an oven at 80 ℃ for 12 hours to remove the N-methyl dipyrrolidone, thus preparing the negative electrode of the lithium ion battery.
The button lithium ion battery (LR 2032) is assembled by the positive electrode, the diaphragm, the electrolyte and the prepared negative electrode, wherein the positive electrode is a metal lithium sheet, and the diaphragm isCelgard 2400 electrolyte 1M LiPF 6 EC/DMC/FEC (volume ratio 1:1:0.1).
Example 2
1. And (3) preparing materials:
(a) Weighing 12g (1 mol) of expanded graphite, putting the expanded graphite into a beaker, adding 100mL of water, stirring for 4 hours in an ultrasonic manner, adding organic silicon tetraethoxysilane with the expanded graphite according to a molar ratio of 1:2, adding 1mL of absolute ethyl alcohol, heating to 80 ℃, and reacting for 4 hours at a stirring rotation speed of 800 r/min; adding ammonia water to adjust the pH to 5, and continuously stirring for 6 hours; filtering, washing and drying to obtain a first precursor H 2 SiO 3 @EG；
(b) First precursor H 2 SiO 3 EG and magnesium powder according to 1: after being uniformly mixed according to the mass ratio, the mixture is placed into a porcelain boat and placed into an Ar atmosphere furnace to be presintered for 5 hours at 250 ℃ and then calcined for 20 hours at 1200 ℃ (the heating rate is 5 ℃/min), and after cooling, the mixture is washed, filtered and dried by dilute hydrochloric acid, and then a precursor second precursor Si@EG is obtained;
(c) Passing the second precursor Si@EG through a 400Kgy dose 60 After Co irradiation source irradiates for 1h, a third precursor Si-xSiO is obtained 2 @EG；
(d) The third precursor Si-xSiO 2 C at 0.3L/min in a CVD furnace 2 H 4 Reacting for 1h at 950 ℃ in atmosphere to obtain Si-xSiO 2 Eg@c composite.
2. Preparation of a lithium ion battery:
mixing 80 parts by weight of the prepared composite material with 10 parts by weight of the conductive agent SP, 10 parts by weight of the binder CMC and SBR (mass ratio of 1:1.5), adding a proper amount of N-methyl dipyrrolidone, continuously stirring until the slurry is uniform, preparing into slurry, coating the slurry on a copper foil current collector (coating thickness is 50-100 mu m) by an automatic coating machine, and vacuum drying in an oven at 80 ℃ for 12 hours to remove the N-methyl dipyrrolidone, thus preparing the negative electrode of the lithium ion battery.
The button lithium ion battery (LR 2032) is assembled by the positive electrode, the diaphragm, the electrolyte and the negative electrode, wherein the positive electrode is a metal lithium sheet, the diaphragm is Celgard 2400, and the electrolyte is 1M LiPF 6 EC/DMC/FEC (volume ratio 1:1:0.1).
Example 3
1. And (3) preparing materials:
(a) Weighing 12g (1 mol) of expanded graphite, putting the expanded graphite into a beaker, adding 100mL of water, stirring for 4 hours in an ultrasonic manner, adding organic silicon tetraethoxysilane with the expanded graphite according to a molar ratio of 1:4, adding 1mL of absolute ethyl alcohol, heating to 80 ℃, and reacting for 4 hours at a stirring rotating speed of 1000 r/min; adding ammonia water to adjust the pH to 5, and continuously stirring for 2 hours; filtering, washing and drying to obtain a first precursor H 2 SiO 3 @EG；
(b) First precursor H 2 SiO 3 EG and magnesium powder according to 4: after being uniformly mixed according to the mass ratio, the mixture is placed into a porcelain boat and placed into an Ar atmosphere furnace to be presintered at 250 ℃ for 5 hours and then calcined at 1200 ℃ for 20 hours (the heating rate is 5 ℃/min), cooled, washed by dilute hydrochloric acid, filtered and dried to obtain a second precursor Si@EG;
(c) Passing the second precursor Si@EG through a 600Kgy dose 60 After Co irradiation source irradiates for 3 hours, a third precursor Si-xSiO is obtained 2 @EG；
(d) The third precursor Si-xSiO 2 C of 0.5L/min of @ EG placed in a CVD furnace 2 H 4 Reacting for 6h at 950 ℃ in atmosphere to obtain Si-xSiO 2 Eg@c composite.
2. Preparation of a lithium ion battery:
mixing 80 parts by weight of the prepared composite material with 10 parts by weight of the conductive agent SP, 10 parts by weight of the binder CMC and SBR (mass ratio of 1:1.5), adding a proper amount of N-methyl dipyrrolidone, continuously stirring until the slurry is uniform, preparing into slurry, coating the slurry on a copper foil current collector (coating thickness is 50-100 mu m) by an automatic coating machine, and vacuum drying in an oven at 80 ℃ for 12 hours to remove the N-methyl dipyrrolidone, thus preparing the negative electrode of the lithium ion battery.
The button lithium ion battery (LR 2032) is assembled by the positive electrode, the diaphragm, the electrolyte and the negative electrode, wherein the positive electrode is a metal lithium sheet, the diaphragm is Celgard 2400, and the electrolyte is 1M LiPF 6 EC/DMC/FEC (volume ratio 1:1:0.1).
Example 4
1. And (3) preparing materials:
(a) 12g (1 mol) of expanded graphite is weighed into a beaker and addedAdding 100mL of water into the mixture, ultrasonically stirring the mixture for 4 hours, adding organic silicon tetraethoxysilane with the expanded graphite according to a molar ratio of 1:2, adding 1mL of absolute ethyl alcohol, heating to 80 ℃, and reacting for 4 hours at a stirring rotating speed of 500 r/min; adding ammonia water to adjust the pH to 5, and continuously stirring for 4 hours; filtering, washing and drying to obtain a first precursor H 2 SiO 3 @EG；
(b) First precursor H 2 SiO 3 EG and magnesium powder according to 4: after being uniformly mixed according to the mass ratio, the mixture is placed into a porcelain boat and placed into an Ar atmosphere furnace to be presintered at 250 ℃ for 5 hours and then calcined at 1200 ℃ for 20 hours (the heating rate is 5 ℃/min), cooled, washed by dilute hydrochloric acid, filtered and dried to obtain a second precursor Si@EG;
(c) Passing the second precursor Si@EG through a 400Kgy dose 60 After Co irradiation source irradiates for 1h, a third precursor Si-xSiO is obtained 2 @EG；
(d) The third precursor Si-xSiO 2 C of @ EG in a CVD furnace at 1L/min 2 H 4 Reacting for 8 hours at 750 ℃ in atmosphere to obtain Si-xSiO 2 Eg@c composite.
2. Preparation of a lithium ion battery:
mixing 80 parts by weight of the prepared composite material with 10 parts by weight of the conductive agent SP, 10 parts by weight of the binder CMC and SBR (mass ratio of 1:1.5), adding a proper amount of N-methyl dipyrrolidone, continuously stirring until the slurry is uniform, preparing into slurry, coating the slurry on a copper foil current collector (coating thickness is 50-100 mu m) by an automatic coating machine, and vacuum drying in an oven at 80 ℃ for 12 hours to remove the N-methyl dipyrrolidone, thus preparing the negative electrode of the lithium ion battery.
The positive electrode, the diaphragm, the electrolyte and the prepared negative electrode are assembled into the button lithium ion battery (LR 2032), wherein the positive electrode is a metal lithium sheet, the diaphragm is Celgard 2400, and the electrolyte is 1M LiPF6 EC/DMC/FEC (volume ratio is 1:1:0.1).
Example 5
1. And (3) preparing materials:
(a) 12g (1 mol) of expanded graphite is weighed and put into a beaker, 100mL of water is added for ultrasonic stirring for 4 hours, organic silicon tetraethoxysilane is added with the expanded graphite according to the mol ratio of 1:4, and meanwhile, 1mL of absolute ethyl alcohol is added, and after heating to 80 ℃, 500r/min stirring is carried outThe rotating speed is reacted for 4 hours; adding ammonia water to adjust the pH to 5, and continuously stirring for 12h; filtering, washing and drying to obtain a first precursor H 2 SiO 3 @EG；
(b) First precursor H 2 SiO 3 EG and magnesium powder according to 1: after being uniformly mixed according to the mass ratio, the mixture is placed into a porcelain boat and placed into an Ar atmosphere furnace to be presintered at 250 ℃ for 5 hours and then calcined at 1200 ℃ for 20 hours (the heating rate is 5 ℃/min), cooled, washed by dilute hydrochloric acid, filtered and dried to obtain a second precursor Si@EG;
(c) Passing the second precursor Si@EG through a dose of 500Kgy 60 After Co irradiation source irradiates for 2 hours, a third precursor Si-xSiO is obtained 2 @EG；
(d) The third precursor Si-xSiO 2 C at 0.56L/min in a CVD furnace 2 H 4 Reacting for 8 hours at 950 ℃ in atmosphere to obtain Si-xSiO 2 Eg@c composite.
2. Preparation of a lithium ion battery:
mixing 80 parts by weight of the prepared composite material, 10 parts by weight of the conductive agent SP and 10 parts by weight of the binder CMC, adding a proper amount of N-methyl dipyrrolidone, continuously stirring until the slurry is uniform, preparing slurry, coating the slurry on a copper foil current collector (the coating thickness is 50-100 mu m) by using an automatic coating machine, and vacuum drying in an oven at 80 ℃ for 12 hours to remove the N-methyl dipyrrolidone, thus preparing the negative electrode of the lithium ion battery.
The button lithium ion battery (LR 2032) is assembled by the positive electrode, the diaphragm, the electrolyte and the negative electrode, wherein the positive electrode is a metal lithium sheet, the diaphragm is Celgard 2400, and the electrolyte is 1M LiPF 6 EC/DMC/FEC (volume ratio 1:1:0.1).
Comparative example 1
1. And (3) preparing materials:
commercial nano-silicon is used as the negative electrode material.
2. Preparation of a lithium ion battery:
mixing 80 parts by weight of the negative electrode material, 10 parts by weight of a conductive agent SP and 10 parts by weight of a binder CMC, adding a proper amount of N-methyl dipyrrolidone, continuously stirring until the slurry is uniform, preparing slurry, coating the slurry on a copper foil current collector (the coating thickness is 50-100 mu m) by an automatic coating machine, and vacuum-drying in an oven at 80 ℃ for 12 hours to remove the N-methyl dipyrrolidone, thus preparing the negative electrode of the lithium ion battery.
The button lithium ion battery (LR 2032) is assembled by the positive electrode, the diaphragm, the electrolyte and the negative electrode, wherein the positive electrode is a metal lithium sheet, the diaphragm is Celgard 2400, and the electrolyte is 1M LiPF 6 EC/DMC/FEC (volume ratio 1:1:0.1).
Comparative example 2
1. Preparing a composite material:
(a) Weighing 12g (1 mol) of expanded graphite, putting the expanded graphite into a beaker, adding 100mL of water, stirring for 4 hours in an ultrasonic manner, adding tetraethoxysilane with the expanded graphite according to a molar ratio of 1:4, heating to 80 ℃ after 1mL of absolute ethyl alcohol, and stirring for 4 hours at a speed of 500 r/min; adding ammonia water to adjust the pH to 5, and continuously stirring for 2 hours; filtering, washing and drying to obtain a first precursor H 2 SiO 3 @EG；
(b) First precursor H 2 SiO 3 EG and magnesium powder according to 1: after being uniformly mixed according to the mass ratio, the mixture is placed into a porcelain boat and placed into an Ar atmosphere furnace to be presintered at 250 ℃ for 5 hours and then calcined at 1200 ℃ for 20 hours (the heating rate is 5 ℃/min), cooled, washed by dilute hydrochloric acid, filtered and dried to obtain a second precursor Si@EG;
(c) Placing a third precursor Si@EG into a CVD furnace for 0.5L/min C 2 H 4 And (3) reacting for 6 hours at 950 ℃ in atmosphere to obtain the Si@EG@C composite material.
2. Preparation of a lithium ion battery:
mixing 80 parts by weight of the prepared composite material with 10 parts by weight of the conductive agent SP, 10 parts by weight of the binder CMC and SBR (mass ratio of 1:1.5), adding a proper amount of N-methyl dipyrrolidone, continuously stirring until the slurry is uniform, preparing into slurry, coating the slurry on a copper foil current collector (coating thickness is 50-100 mu m) by an automatic coating machine, and vacuum drying in an oven at 80 ℃ for 12 hours to remove the N-methyl dipyrrolidone, thus preparing the negative electrode of the lithium ion battery.
The LR2032 button lithium ion battery is assembled by the positive electrode, the diaphragm, the electrolyte and the prepared negative electrode, wherein the positive electrode is a metal lithium sheet, the diaphragm is Celgard 2400, and the electrolyte is 1M LiPF 6 EC/DMC/FEC (volume ratio 1:1:0.1).
Test examples
The lithium ion batteries assembled in examples 1-5 and comparative examples 1-2 were subjected to electrochemical performance testing at 0-2.0V voltage and 0.1C/0.1C current.
Si-xSiO of example 1 2 The electrical properties of the @ EG @ C composite are shown in FIG. 1.
The test results of each example and comparative example are shown in table 1:
TABLE 1 comparison of electrochemical Properties results
By comparing the example 1 with the comparative example 1, the lithium ion battery assembled by the invention can greatly improve the capacity retention rate after circulation and has excellent electrochemical performance. Comparing example 1 with comparative example 2, it can be seen that the volume expansion is significantly reduced after the oxide layer is formed on the silicon surface, and the cycle performance is significantly improved.
The present invention is described in detail above. It will be apparent to those skilled in the art that the present invention may be practiced in a wide variety of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the invention. While the invention has been described with respect to specific embodiments, it will be appreciated that the invention may be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains.
Claims (10)
1. A preparation method of a composite anode material for a lithium ion battery is characterized in that the composite material is Si-xSiO 2 Eg@c comprising the steps of:
s1, adding water into expanded graphite, ultrasonically stirring, sequentially adding organic silicon and ethanol for a first reaction, and adjusting the pH value for a second reaction to obtain a first precursor H 2 SiO 3 @EG；
S2, mixing the first precursor and magnesium powder, and then calcining the mixture in an inert atmosphere to obtain a second precursor Si@EG;
s3, carrying out the second precursor 60 Co irradiation source irradiation to obtain a third precursor Si-xSiO 2 @EG；
And S4, performing chemical vapor deposition on the third precursor in an ethylene atmosphere to perform carbon coating, so as to obtain the composite anode material for the lithium ion battery.
2. The method of manufacturing according to claim 1, characterized in that: the organic silicon is one or more of tetraethoxysilane and silicon tetrachloride.
3. The method of manufacturing according to claim 1, characterized in that: the molar ratio of the organosilicon to the expanded graphite is 1: (0.1-20);
the mass ratio of the expanded graphite to the water is (1-20): 100;
the ratio of the expanded graphite to the ethanol is 1mol: (0.2-20) mL.
4. The method of manufacturing according to claim 1, characterized in that: the temperature of the first reaction in the step (1) is 40-100 ℃ and the time is 2-8 h;
the first reaction is carried out under the stirring condition, and the stirring rotating speed is 500-1000 r/min.
5. The method of manufacturing according to claim 1, characterized in that: the pH value is adjusted to 3-8 by ammonia water;
the temperature of the second reaction is 40-100 ℃ and the time is 2-12 h;
the second reaction is carried out under the stirring condition, and the stirring rotating speed is 500-1000 r/min.
6. The method of manufacturing according to claim 1, characterized in that: the mass ratio of the first precursor to the magnesium powder is 1: (0.1-2);
the calcination treatment is that the calcination is carried out for 4 to 8 hours at 150 to 250 ℃ and then for 8 to 24 hours at 800 to 1200 ℃.
7. The method of manufacturing according to claim 1, characterized in that: the said 60 The irradiation dose of the Co irradiation source is 10-1000 Kgy, and the irradiation time is 0.1-10 h.
8. The method of manufacturing according to claim 1, characterized in that: the flow of the ethylene is 0.1-1L/min;
the temperature of the chemical vapor deposition is 600-1000 ℃ and the time is 1-12 h.
9. The composite anode material for lithium ion batteries prepared by the preparation method of any one of claims 1 to 8.
10. A lithium ion battery comprising a positive electrode piece, a negative electrode piece, a diaphragm and electrolyte, wherein the negative electrode piece comprises a current collector and the composite negative electrode material for the lithium ion battery of claim 9 loaded on the current collector.
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