CN110459752A - A kind of anode material of lithium-ion battery and its preparation method and application - Google Patents
A kind of anode material of lithium-ion battery and its preparation method and application Download PDFInfo
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- CN110459752A CN110459752A CN201910806554.3A CN201910806554A CN110459752A CN 110459752 A CN110459752 A CN 110459752A CN 201910806554 A CN201910806554 A CN 201910806554A CN 110459752 A CN110459752 A CN 110459752A
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- Prior art keywords
- ion battery
- lithium
- anode material
- molybdenum
- preparation
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 63
- 239000010405 anode material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 69
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 65
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 65
- 239000011733 molybdenum Substances 0.000 claims abstract description 65
- 239000002135 nanosheet Substances 0.000 claims abstract description 32
- 238000011065 in-situ storage Methods 0.000 claims abstract description 20
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- 239000004202 carbamide Substances 0.000 claims description 16
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 14
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 13
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 238000009831 deintercalation Methods 0.000 abstract description 2
- 238000003780 insertion Methods 0.000 abstract description 2
- 230000037431 insertion Effects 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 238000001816 cooling Methods 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 229910052718 tin Inorganic materials 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 16
- 239000012300 argon atmosphere Substances 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 14
- 239000007773 negative electrode material Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000002604 ultrasonography Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000008030 elimination Effects 0.000 description 7
- 238000003379 elimination reaction Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000012265 solid product Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011684 sodium molybdate Substances 0.000 description 6
- 235000015393 sodium molybdate Nutrition 0.000 description 6
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 6
- 210000000988 bone and bone Anatomy 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 241000628997 Flos Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- -1 melamine Amine Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- 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
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
-
- 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
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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 present invention relates to electrode material technical fields more particularly to a kind of anode material of lithium-ion battery and preparation method thereof.Anode material of lithium-ion battery provided by the invention, the molybdenum doping tin dioxide nanosheet array including sponge carbon and growth in situ on the sponge carbon backbone structure；The mass percent that the molybdenum doping tin dioxide nanosheet array accounts for the anode material of lithium-ion battery is 30~45%.The present invention additionally aids the volume expansion for alleviating that stannic oxide occurs in cyclic process using sponge carbon as conducting matrix grain.Doping molybdenum improves the electric conductivity of stannic oxide in stannic oxide simultaneously, accelerates transmission of the sodium ion in the anode material of lithium-ion battery.Nanometer sheet increases the contact area of composite material and electrolyte, so that the insertion and deintercalation of sodium ion are more abundant.Record according to the embodiment, anode material of lithium-ion battery of the present invention have good cycle performance and high rate performance.
Description
Technical field
The present invention relates to electrode material technical fields more particularly to a kind of anode material of lithium-ion battery and preparation method thereof
And application.
Background technique
With the continuous development of global economy, the continuous improvement of living standards of the people, energy and environmental problem is also increasingly prominent
Out.As the carrier of electric energy storage, lithium ion secondary battery is due to energy density height, having extended cycle life, self discharge effect
The advantages such as small, environmentally friendly have been widely used in the fields such as mobile phone, digital portable product.However since lithium is on ground
Resource on ball is limited, and people begin look for substitute the new energy battery of lithium ion battery.In this context, sodium from
Son is due to having physical and chemical properties similar with lithium ion, while earth reserves are big, at low cost, and is considered as lithium ion
Potential substitute.
Since the radius ratio lithium ion of sodium ion is big, conventional graphite cathode can not accommodate sodium ion at all.Therefore, it finds and closes
Suitable anode material of lithium-ion battery is extremely important.In recent years, metal oxide, especially tin oxide are due to its high specific capacity
And it is widely paid close attention to.But the electric conductivity of stannic oxide itself is not strong, charge and discharge cycles are in the process along with biggish body
Product expansion, significantly limits the application of negative electrode material carried out by it in the battery.
In view of the above-mentioned problems, being presently mainly strong carbon or to be led by the negative electrode material of Nanostructure fabrication, with electric conductivity
Electric polymer is compound and the modes such as doping are alleviated.However it is needed by the negative electrode material that above-mentioned alleviation mode obtains coated in collection
Charge and discharge can be participated in as cathode on fluid.
Summary of the invention
The purpose of the present invention is to provide a kind of anode material of lithium-ion battery and its preparation method and application, the sodium from
Sub- cell negative electrode material also has while with good electric conductivity, electrochemical cycle stability and high rate performance from branch
Support effect, just can participate in charge and discharge without being coated on collector.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of anode material of lithium-ion batteries, including sponge carbon and growth in situ are in the sponge carbon bone
Molybdenum doping tin dioxide nanosheet array in frame structure；
The molybdenum doping tin dioxide nanosheet account for the anode material of lithium-ion battery mass percent be 30~
45%.
Preferably, according to atomic percentage, in the anode material of lithium-ion battery, the atomic percent of molybdenum is 0.5
~1.5%.
The present invention also provides the preparation method of the anode material of lithium-ion battery described in above-mentioned technical proposal, including it is following
Step:
Tin source, molybdenum source, concentrated hydrochloric acid, thioacetic acid, urea and water are mixed, mixed solution is obtained；
Sponge carbon is placed in the mixed solution, hydro-thermal reaction and sintering is successively carried out, obtains sodium-ion battery cathode
Material.
Preferably, the molar ratio of the tin source and molybdenum source is (1.0~1.6): (0.05~0.35)；
The tin source is in terms of tin, and the molybdenum source is in terms of molybdenum.
Preferably, the mass concentration of the concentrated hydrochloric acid is 37%；
The urea, thioacetic acid, concentrated hydrochloric acid, tin source and water amount ratio be (0.8~1.2) g:(18~22) μ L:
(0.8~1.2) mL:(1.0~1.1) mmol:(75~85) mL；
The tin source is in terms of tin.
Preferably, the amount ratio of the sponge carbon and the mixed solution is (1.2~5.6) g:(70~80) mL.
Preferably, the temperature of the hydro-thermal reaction is 110~130 DEG C, and the time of the hydro-thermal reaction is 8~12h.
Preferably, the sintering carries out in protective atmosphere；
The temperature of the sintering is 450~650 DEG C, and heating rate is 1~2 DEG C/min, and the soaking time of the sintering is 2
~5h.
Preferably, the sponge carbon preparation method the following steps are included:
Under an inert atmosphere, melamine sponge is subjected to high temperature cabonization, obtains sponge carbon；
The temperature of the high temperature cabonization is 750~850 DEG C, and heating rate is 4.5~5.5 DEG C/min, the high temperature cabonization
Soaking time be 1~3 hour；
Before the sponge carbon is placed in the mixed solution, hydrophilic treated is carried out to sponge carbon.
The present invention also provides the anode material of lithium-ion battery described in above-mentioned technical proposal or by above-mentioned technical proposal institute
Application of the anode material of lithium-ion battery that the preparation method stated is prepared in sodium-ion battery.
The present invention provides a kind of anode material of lithium-ion batteries, including sponge carbon and growth in situ are in the sponge carbon bone
Molybdenum doping tin dioxide nanosheet array in frame structure；The molybdenum doping tin dioxide nanosheet array accounts for the sodium ion electricity
The mass percent of pond negative electrode material is 30~45%.The present invention guarantees to play from branch using sponge carbon as conducting matrix grain
Support effect, so that it when as electrode material, on a current collector without coating, additionally aids and alleviate two in cyclic process
The volume expansion that tin oxide occurs.Doping molybdenum improves the electric conductivity of stannic oxide in stannic oxide simultaneously, accelerates sodium ion
Transmission in the anode material of lithium-ion battery.Nanometer sheet increases the contact area of composite material and electrolyte, so that
The insertion and deintercalation of sodium ion are more abundant.Record according to the embodiment, anode material of lithium-ion battery tool of the present invention
There are good cycle performance and high rate performance.
Detailed description of the invention
Fig. 1 be the sponge carbon that is prepared of embodiment 1 in the SEM figure under different multiples (a is the SEM figure under 10 multiples, b
For the SEM figure under 20 multiples)；
Fig. 2 is that (a is 10 multiples to SEM figure of the anode material of lithium-ion battery that is prepared of embodiment 1 under different multiples
Under SEM figure, b be 20 multiples under SEM figure, c be 100 multiples under SEM figure)；
Fig. 3 is that (a is 200 times to TEM figure of the anode material of lithium-ion battery that is prepared of embodiment 1 under different multiples
TEM figure under several, b are the TEM figure under 1000 multiples, and c is the EDS figure under 50 multiples tested under TEM)；
XRD diagram of the anode material of lithium-ion battery that Fig. 4 embodiment 1 is prepared under different multiples；
Fig. 5 is that the anode material of lithium-ion battery that embodiment 1 is prepared exists as the sodium-ion battery of negative electrode material
0.1A·g-1、0.2A·g-1、0.5A·g-1、1A·g-1Current density under high rate performance figure；
Fig. 6 is that the anode material of lithium-ion battery that embodiment 1 is prepared exists as the sodium-ion battery of negative electrode material
0.1A·g-1Current density under circulation 100 circle discharge capacity and coulombic efficiency figure.
Specific embodiment
The present invention provides a kind of anode material of lithium-ion batteries, including sponge carbon and growth in situ are in the sponge carbon bone
Molybdenum doping tin dioxide nanosheet array in frame structure；
The mass percent that the molybdenum doping tin dioxide nanosheet array accounts for the anode material of lithium-ion battery is 30
~45%.
In the present invention, the anode material of lithium-ion battery includes sponge carbon；Three-dimensional conductive bone is presented in the sponge carbon
Frame structure.In the present invention, the mass percent that the sponge carbon accounts for the anode material of lithium-ion battery is preferably 55~
70%, more preferably 60~65%.
In the present invention, the anode material of lithium-ion battery further includes growth in situ on the sponge carbon backbone structure
Molybdenum doping tin dioxide nanosheet array；The molybdenum doping tin dioxide nanosheet array is by molybdenum doping tin dioxide nanosheet
It is intertwined (such as structure shown in Fig. 3).In the present invention, the staggered molybdenum doping tin dioxide nanosheet
It is more advantageous to the contact area for increasing negative electrode material and electrolyte, alleviates the polymerization of tin to a certain extent.In the present invention,
The thickness of the molybdenum doping tin dioxide nanosheet is preferably 10~15nm, more preferably 11~14nm, most preferably 12~
13nm.The partial size of the molybdenum doping tin dioxide nanosheet is preferably 15~40nm, more preferably 18~35nm, most preferably 20
~30nm.In the present invention, the molybdenum doping tin dioxide nanosheet array accounts for the quality of the anode material of lithium-ion battery
Percentage is preferably 30~45%, and more preferably 35~40%.According to atomic percentage, the molybdenum doping stannic oxide nanometer
In chip arrays, percentage of the molybdenum in the anode material of lithium-ion battery is preferably 0.5~1.5%, more preferably 0.8~
1.2%.The molybdenum exists in the form of substituting part tin atom site.
The present invention also provides the preparation method of the anode material of lithium-ion battery described in above-mentioned technical proposal, including it is following
Step:
Tin source, molybdenum source, concentrated hydrochloric acid, thioacetic acid, urea and water are mixed, mixed solution is obtained；
Sponge carbon is placed in the mixed solution, hydro-thermal reaction and sintering is successively carried out, obtains sodium-ion battery cathode
Material.
In the present invention, if without specified otherwise, all raw materials are commercial product well known to those skilled in the art.
The present invention mixes tin source, molybdenum source, concentrated hydrochloric acid, thioacetic acid, urea and water, obtains mixed solution；In the present invention
In, the tin source is preferably stannous chloride, and the stannous chloride is preferably stannous chloride dihydrate and/or anhydrous stannous chloride, more
Preferably stannous chloride dihydrate.
In the present invention, the molybdenum source is preferably one or more of Sodium Molybdate Dihydrate, ammonium heptamolybdate and molybdenum chloride；When
The molybdenum source be above-mentioned specific choice in it is two or more when, the present invention to the specific substance proportion it is no any special
It limits, is mixed by any proportion；When the molybdenum source is one of above-mentioned specific choice, the molybdenum source is more preferable
For Sodium Molybdate Dihydrate.In the present invention, the mass concentration of the concentrated hydrochloric acid is preferably 37%.
In the present invention, the mixing preferably carries out under stirring conditions, and the present invention is to the no any spy of stirring
Different restriction is carried out by whipping process well known to those skilled in the art.
In the present invention, the mixing of the tin source, molybdenum source, concentrated hydrochloric acid, thioacetic acid, urea and water preferably in water according to
Secondary addition urea, thioacetic acid and concentrated hydrochloric acid to uniformly after, sequentially add tin source and molybdenum source.
In the present invention, the molar ratio of the tin source and molybdenum source is preferably (1.0~1.6): (0.05~0.35), more preferably
For (1.1~1.5): (0.09~0.3), most preferably (1.2~1.3): (0.1~0.2)；The tin source is preferably in terms of tin, institute
Molybdenum source is stated preferably in terms of molybdenum.In the present invention, the amount ratio of the urea, thioacetic acid, concentrated hydrochloric acid, tin source and water is preferably
(0.8~1.2) g:(18~22) L:(0.8~1.2 μ) mL:(1.0~1.1) mmol:(75~85) mL, more preferably (0.9~
1.1) g:(19~21) L:(0.9~1.1 μ) mL:(1.02~1.08) mmol:(78~82) mL, most preferably 1g:20 μ L:
1mL:1.05mmol:80mL.
In the present invention, the effect of the urea is to provide amino, and the effect of the thioacetic acid is to react to give birth to amino
At reactive species, the effect of the concentrated hydrochloric acid is the pH for adjusting solution.
After obtaining mixed solution, sponge carbon is placed in the mixed solution by the present invention, successively carries out hydro-thermal reaction and burning
Knot, obtains anode material of lithium-ion battery.
In the present invention, the preparation method of the sponge carbon preferably includes following steps: under an inert atmosphere, by melamine
Amine sponge carries out high temperature cabonization, obtains sponge carbon.In the present invention, before carrying out high temperature cabonization, preferably to the melamine sea
Silk floss is pre-processed；The pretreatment is dry after preferably being cleaned the melamine sponge using ethyl alcohol；In this hair
In bright, the cleaning is preferably carried out under conditions of ultrasound, and the time of the ultrasound is preferably 10~20min, and more preferably 12
~18min, most preferably 15min.In the present invention, the drying is preferably dried in vacuo, and the present invention is to the vacuum drying
Condition does not have any special restriction, using vacuum drying condition well known to those skilled in the art.
In the present invention, the inert atmosphere is preferably argon atmosphere or nitrogen atmosphere, and the temperature of the high temperature cabonization is excellent
It is selected as 750~850 DEG C, more preferably 780~820 DEG C, most preferably 800 DEG C；Heating rate is preferably 4.5~5.5 DEG C/min,
More preferably 4.8~5.2 DEG C/min, most preferably 5.0 DEG C/min；Soaking time is preferably 0.5~3 hour, more preferably 1.0
~2.0h, most preferably 1.0h.
In the present invention, before the obtained sponge carbon being placed in the mixed solution, preferably to the sponge carbon into
Row hydrophilic treated, the hydrophilic treated are preferably corona treatment.The present invention does not have any spy to the corona treatment
Different restriction is carried out using process well known in the art.Detailed process is preferred in an embodiment of the present invention are as follows: by sponge
Carbon is placed in plasma instrument, and air pressure is evacuated to 1*10-5Plasma gas is opened afterwards and is switched starts hydrophilic treated, processing 10~
Plasma gas switch is closed after 20min, after gas in cabin is returned to atmospheric pressure, takes out sample.
After the completion of hydrophilic treated, the present invention is preferably adequately soaked the sponge carbon after hydrophilic treated in hydrochloric acid solution
Stain, to remove extra impurity；In the present invention, the concentration of the hydrochloric acid solution is preferably 1mol/L；The temperature of the dipping
Preferably 20~30 DEG C, more preferably 22~28 DEG C, most preferably 25 DEG C；The time of the dipping is preferably 20~30h, more excellent
It is selected as 22~28h, most preferably 24~26h.
In the present invention, the amount ratio of the sponge carbon and mixed solution is preferably (1.2~5.6) g:(70~80) mL,
More preferably (2.4~5.6) g:(70~80) mL, most preferably (4.8~5.6) g:(70~80) mL.
In the present invention, the temperature of the hydro-thermal reaction is preferably 110~130 DEG C, more preferably 115~125 DEG C, optimal
120 DEG C are selected as, the time of the hydro-thermal reaction is preferably 10~15h, more preferably 11~14h, most preferably 12~13h.In
In the present invention, the hydro-thermal reaction carries out preferably in hydrothermal reaction kettle, and the material of the inner liner of reaction kettle is preferably tetrafluoro second
Alkene.
After the completion of the hydro-thermal reaction, the present invention, which has, cools down the product system after hydro-thermal reaction, the cooling
Mode is preferably water cooling.After cooling, the present invention is preferably filtered, cleans and dries to obtained product system, the present invention couple
The no any special restriction of filtering, is carried out by process well known to those skilled in the art；The cleaning is preferably
Filtered solid product is cleaned with deionized water and ethyl alcohol, the sodium hydroxide solution impurity elimination of 1mol/L is used at 45 DEG C
10h；The present invention any special restriction no to the drying is using drying process well known to those skilled in the art
It can.
In the present invention, the process of the hydro-thermal reaction is growth in situ tin dioxide nanosheet array doping molybdenum simultaneously
Process can realize simultaneously two processes of growth in situ and doping in water-heat process.
In the present invention, the sintering carries out preferably in protective atmosphere, and in the present invention, the protective atmosphere is preferably
Argon atmosphere or nitrogen atmosphere.In the present invention, the temperature of the sintering is preferably 450~550 DEG C, more preferably 480~520
DEG C, most preferably 500 DEG C；Heating rate is preferably 0.8~1.2 DEG C/min, more preferably 0.9~1.1 DEG C/min, most preferably
1.0℃/min；In the present invention, the temperature-rise period preferably at the uniform velocity heats up；The soaking time of the sintering is preferably 2~
5h, more preferably 3~4h, most preferably 3h.
In the present invention, the process of the sintering improves the crystallinity of product, enhances its electric conductivity, facilitates electrification
The shuttle for learning sodium ion in reaction process, to improve battery high rate performance.
After the completion of the sintering, sintered product is preferably carried out cooling treatment by the present invention, and the present invention is to the cooling
There is no any special restriction, is carried out using process well known to those skilled in the art cooling.
The present invention also provides the anode material of lithium-ion battery described in above-mentioned technical proposal or by above-mentioned technical proposal institute
Application of the anode material of lithium-ion battery that the preparation method stated is prepared in sodium-ion battery.
In the present invention, the application is preferably by the anode material of lithium-ion battery directly as cathode and sodium piece group
Dress up the button cell of model CR 2025；The electrolyte of the button cell preferably contains 5vol%FEC, EC:DEC volume
Than the 1MNaClO for 1:14Solution；The diaphragm of the button cell is preferably commercial fiber glass filter paper (Whatman GF/F).
Anode material of lithium-ion battery provided by the invention and its preparation method and application is carried out below with reference to embodiment
Detailed description, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Under stirring conditions, 1g urea, 20 μ L thioacetic acid and 1mL 37wt% will be sequentially added in 80mL water
Concentrated hydrochloric acid to uniformly after, sequentially add 0.238g (0.00105mol) stannous chloride dihydrate and 0.022g (0.00009mol) two
Water sodium molybdate, obtains mixed liquor；
Under ultrasound condition, after melamine sponge is cleaned 15min with ethyl alcohol, vacuum drying；Under an argon atmosphere, with
The heating rate of 5 DEG C/min rises to 800 DEG C, cooling after carrying out high temperature cabonization 1h；By product after cooling in plasma gas
After carrying out hydrophilic treated, it is immersed in the HCl solution of 1mol/L, it is dry after being impregnated for 24 hours at 35 DEG C, obtain sponge carbon；
The sponge carbon (5.6g) of 4cm*1cm*0.5cm size is placed in 80mL mixed liquor, progress hydro-thermal reaction (120 DEG C,
After 12h), water cooling and filtering are successively carried out, and cleaned to filtered solid product with deionized water and ethyl alcohol, at 45 DEG C
The lower sodium hydroxide solution impurity elimination 10h with 1mol/L, it is dry, obtain the molybdenum doping tin dioxide nanosheet of sponge carbon growth in situ
Array；
In argon atmosphere, the molybdenum doping tin dioxide nanosheet array of the sponge carbon growth in situ is sintered place
After managing (rise to 500 DEG C with the heating rate of 1 DEG C/min, and keep the temperature 3h), it is cooled to room temperature, obtains anode material of lithium-ion battery
(load capacity of nanometer sheet is 38%, 1%) doping of molybdenum is.
The sponge carbon and the anode material of lithium-ion battery are subjected to SEM test, test result such as Fig. 1 and Fig. 2 institute
Show, wherein for the sponge carbon, in the SEM figure under different multiples, (a is the SEM figure under 10 multiples to Fig. 1, and b is the SEM under 30 multiples
Figure), as shown in Figure 1, the pattern of sponge carbon is three-dimensional self-supporting network structure, skeleton smooth surface；Fig. 2 is the sodium ion electricity
In the SEM figure under different multiples, (a is the SEM figure under 10 multiples to pond negative electrode material, and b is the SEM figure under 30 multiples, and c is 100 times
SEM figure under several), as shown in Figure 2, the tin dioxide nanosheet array of molybdenum doping is uniform in the anode material of lithium-ion battery
Be grown on the skeleton of sponge carbon, the tin dioxide nanosheet of the molybdenum doping with a thickness of 10nm；
The anode material of lithium-ion battery is subjected to TEM test, (a is the TEM under 200 multiples by test result such as Fig. 3
Figure, b are the TEM figure under 1000 multiples, and c is the EDS figure under TEM under 50 multiples tested) shown in, wherein figure c by it is left extremely
The right side, the upper left corner respectively indicate icon c, carbon, tin element, oxygen element and molybdenum element；From the figure 3, it may be seen that the two of the molybdenum doping
The interlaced formation array of tin oxide nano piece, and interplanar distance interplanar distance corresponding with stannic oxide is coincide；
The anode material of lithium-ion battery is subjected to XRD test, test results are shown in figure 4, as shown in Figure 4, described
The crystallographic plane diffraction peak of sodium ion negative electrode material matches with the crystal face of stannic oxide.
Embodiment 2
Under stirring conditions, 1g urea, 20 μ L thioacetic acid and 1mL 37wt% will be sequentially added in 80mL water
Concentrated hydrochloric acid to uniformly after, sequentially add 0.357g (0.00158mol) stannous chloride dihydrate and 0.022g (0.00009mol) two
Water sodium molybdate, obtains mixed liquor；
Under ultrasound condition, after melamine sponge is cleaned 15min with ethyl alcohol, vacuum drying；Under an argon atmosphere, with
The heating rate of 5 DEG C/min rises to 800 DEG C, cooling after carrying out high temperature cabonization 1h；By product after cooling in plasma gas
After carrying out hydrophilic treated, it is immersed in the HCl solution of 1mol/L, it is dry after being impregnated for 24 hours at 35 DEG C, obtain sponge carbon；
The sponge carbon (5.2g) of 4cm*1cm*0.5cm size is placed in 80mL mixed liquor, progress hydro-thermal reaction (120 DEG C,
After 12h), water cooling and filtering are successively carried out, and cleaned to filtered solid product with deionized water and ethyl alcohol, at 45 DEG C
The lower sodium hydroxide solution impurity elimination 10h with 1mol/L, it is dry, obtain the molybdenum doping tin dioxide nanosheet of sponge carbon growth in situ
Array；
In argon atmosphere, the molybdenum doping tin dioxide nanosheet array of the sponge carbon growth in situ is sintered place
After managing (rise to 500 DEG C with the heating rate of 1 DEG C/min, and keep the temperature 3h), it is cooled to room temperature, obtains anode material of lithium-ion battery
(load capacity of nanometer sheet is 43.5%, 0.8%) doping of molybdenum is.
Embodiment 3
Under stirring conditions, 1g urea, 20 μ L thioacetic acid and 1mL 37wt% will be sequentially added in 80mL water
Concentrated hydrochloric acid to uniformly after, sequentially add 0.238g (0.00105mol) stannous chloride dihydrate and 0.022g (0.00009mol) two
Water sodium molybdate, obtains mixed liquor；
Under ultrasound condition, after melamine sponge is cleaned 15min with ethyl alcohol, vacuum drying；Under an argon atmosphere, with
The heating rate of 5 DEG C/min rises to 800 DEG C, cooling after carrying out high temperature cabonization 1h；By product after cooling in plasma gas
After carrying out hydrophilic treated, it is immersed in the HCl solution of 1mol/L, it is dry after being impregnated for 24 hours at 35 DEG C, obtain sponge carbon；
The sponge carbon (5.6g) of 4cm*1cm*0.5cm size is placed in 80mL mixed liquor, progress hydro-thermal reaction (120 DEG C,
After 8h), water cooling and filtering are successively carried out, and cleaned to filtered solid product with deionized water and ethyl alcohol, at 45 DEG C
The lower sodium hydroxide solution impurity elimination 10h with 1mol/L, it is dry, obtain the molybdenum doping tin dioxide nanosheet of sponge carbon growth in situ
Array；
In argon atmosphere, the molybdenum doping tin dioxide nanosheet array of the sponge carbon growth in situ is sintered place
After managing (rise to 500 DEG C with the heating rate of 1 DEG C/min, and keep the temperature 3h), it is cooled to room temperature, obtains anode material of lithium-ion battery
(load capacity of nanometer sheet is 36%, 1.2%) doping of molybdenum is.
Embodiment 4
Under stirring conditions, 1g urea, 20 μ L thioacetic acid and 1mL 37wt% will be sequentially added in 80mL water
Concentrated hydrochloric acid to uniformly after, sequentially add 0.238g (0.00105mol) stannous chloride dihydrate and 0.08g (0.00035mol) two
Water sodium molybdate, obtains mixed liquor；
Under ultrasound condition, after melamine sponge is cleaned 15min with ethyl alcohol, vacuum drying；Under an argon atmosphere, with
The heating rate of 5 DEG C/min rises to 800 DEG C, cooling after carrying out high temperature cabonization 1h；By product after cooling in plasma gas
After carrying out hydrophilic treated, it is immersed in the HCl solution of 1mol/L, it is dry after being impregnated for 24 hours at 35 DEG C, obtain sponge carbon；
The sponge carbon (5.6g) of 4cm*1cm*0.5cm size is placed in 80mL mixed liquor, progress hydro-thermal reaction (120 DEG C,
After 12h), water cooling and filtering are successively carried out, and cleaned to filtered solid product with deionized water and ethyl alcohol, at 45 DEG C
The lower sodium hydroxide solution impurity elimination 10h with 1mol/L, it is dry, obtain the molybdenum doping tin dioxide nanosheet of sponge carbon growth in situ
Array；
In argon atmosphere, the molybdenum doping tin dioxide nanosheet array of the sponge carbon growth in situ is sintered place
After managing (rise to 500 DEG C with the heating rate of 1 DEG C/min, and keep the temperature 3h), it is cooled to room temperature, obtains anode material of lithium-ion battery
(load capacity of nanometer sheet is 35%, 3%) doping of molybdenum is.
Embodiment 5
Under stirring conditions, 1g urea, 20 μ L thioacetic acid and 1mL 37wt% will be sequentially added in 80mL water
Concentrated hydrochloric acid to uniformly after, sequentially add 0.238g (0.0015mol) stannous chloride dihydrate and 0.022g (0.00009mol) two
Water sodium molybdate, obtains mixed liquor；
Under ultrasound condition, after melamine sponge is cleaned 15min with ethyl alcohol, vacuum drying；Under an argon atmosphere, with
The heating rate of 5 DEG C/min rises to 600 DEG C, cooling after carrying out high temperature cabonization 3h；By product after cooling in plasma gas
After carrying out hydrophilic treated, it is immersed in the HCl solution of 1mol/L, it is dry after being impregnated for 24 hours at 35 DEG C, obtain sponge carbon；
The sponge carbon (4.8g) of 4cm*1cm*0.5cm size is placed in 80mL mixed liquor, progress hydro-thermal reaction (120 DEG C,
After 12h), water cooling and filtering are successively carried out, and cleaned to filtered solid product with deionized water and ethyl alcohol, at 45 DEG C
The lower sodium hydroxide solution impurity elimination 10h with 1mol/L, it is dry, obtain the molybdenum doping tin dioxide nanosheet of sponge carbon growth in situ
Array；
In argon atmosphere, the molybdenum doping tin dioxide nanosheet array of the sponge carbon growth in situ is sintered place
After managing (rise to 500 DEG C with the heating rate of 1 DEG C/min, and keep the temperature 3h), it is cooled to room temperature, obtains anode material of lithium-ion battery
(load capacity of nanometer sheet is 36%, 1%) doping of molybdenum is.
Embodiment 6
Under stirring conditions, 1g urea, 20 μ L thioacetic acid and 1mL 37wt% will be sequentially added in 80mL water
Concentrated hydrochloric acid to uniformly after, sequentially add 0.238g (0.0015mol) stannous chloride dihydrate and 0.022g (0.00009mol) two
Water sodium molybdate, obtains mixed liquor；
Under ultrasound condition, after melamine sponge is cleaned 15min with ethyl alcohol, vacuum drying；Under an argon atmosphere, with
The heating rate of 5 DEG C/min rises to 800 DEG C, cooling after carrying out high temperature cabonization 1h；By product after cooling in plasma gas
After carrying out hydrophilic treated, it is immersed in the HCl solution of 1mol/L, it is dry after being impregnated for 24 hours at 35 DEG C, obtain sponge carbon；
The sponge carbon (5.4g) of 4cm*1cm*0.5cm size is placed in 80mL mixed liquor, progress hydro-thermal reaction (120 DEG C,
After 12h), water cooling and filtering are successively carried out, and cleaned to filtered solid product with deionized water and ethyl alcohol, at 45 DEG C
The lower sodium hydroxide solution impurity elimination 10h with 1mol/L, it is dry, obtain the molybdenum doping tin dioxide nanosheet of sponge carbon growth in situ
Array；
In argon atmosphere, the molybdenum doping tin dioxide nanosheet array of the sponge carbon growth in situ is sintered place
After managing (rise to 600 DEG C with the heating rate of 2 DEG C/min, and keep the temperature 2h), it is cooled to room temperature, obtains anode material of lithium-ion battery
(load capacity of nanometer sheet is 38%, 1%) doping of molybdenum is.
Application examples
Anode material of lithium-ion battery described in embodiment 1 is assembled into model CR 2025 directly as cathode and sodium piece
Button cell (electrolyte is containing 5vol%FEC, and EC:DEC volume ratio is the 1MNaClO of 1:14Solution, diaphragm are commercial glass
Fiber filter paper (Whatman GF/F)), and test its chemical property:
Fig. 5 is the button cell in 0.1Ag-1、0.2A·g-1、0.5A·g-1、1A·g-1Current density under times
Rate performance map, as shown in Figure 5, the button cell, with the increase of current density, the capacity of battery only has subtracting by a small margin
It is few, there is preferable high rate performance.In 0.1Ag-1、0.2A·g-1、0.5A·g-1、1A·g-1Current density under, battery hold
Amount is respectively 1143mAhg-1,570mAh·g-1,451mAh·g-1,336mAh·g-1。
Fig. 6 is the button cell in 0.1Ag-1Current density under circulation 100 circle discharge capacity and coulombic efficiency
Figure, it will be appreciated from fig. 6 that the initial discharge capacity of the button cell is 1017.11mAhg-1, 100 times circulation after discharge capacity
For 575mAhg-1, coulombic efficiency holding 99.3%, battery capacity does not decline substantially, or even has mild activation, and explanation has
Good cycle performance.
Structured testing and electrochemical property test are carried out to the anode material of lithium-ion battery of embodiment 2~6 respectively, tied
Structure is consistent with the structure of anode material of lithium-ion battery described in embodiment 1；Sodium-ion battery described in chemical property and embodiment 1
The test result of negative electrode material is similar, all has good cycle performance and high rate performance.
As seen from the above embodiment, anode material of lithium-ion battery provided by the invention have good cycle performance and times
Rate performance.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of anode material of lithium-ion battery, which is characterized in that including sponge carbon and growth in situ in the sponge carbon skeleton
Molybdenum doping tin dioxide nanosheet array in structure；
The mass percent that the molybdenum doping tin dioxide nanosheet accounts for the anode material of lithium-ion battery is 30~45%.
2. anode material of lithium-ion battery as described in claim 1, which is characterized in that according to atomic percentage, the sodium
In ion battery cathode material, the atomic percent of molybdenum is 0.5~1.5%.
3. the preparation method of anode material of lithium-ion battery of any of claims 1 or 2, which comprises the following steps:
Tin source, molybdenum source, concentrated hydrochloric acid, thioacetic acid, urea and water are mixed, mixed solution is obtained；
Sponge carbon is placed in the mixed solution, hydro-thermal reaction and sintering is successively carried out, obtains anode material of lithium-ion battery.
4. preparation method as claimed in claim 3, which is characterized in that the molar ratio of the tin source and molybdenum source be (1.0~
1.6): (0.05~0.35)；
The tin source is in terms of tin, and the molybdenum source is in terms of molybdenum.
5. preparation method as claimed in claim 3, which is characterized in that the mass concentration of the concentrated hydrochloric acid is 37%；
The urea, thioacetic acid, concentrated hydrochloric acid, tin source and water amount ratio be (0.8~1.2) g:(18~22) μ L:(0.8~
1.2) mL:(1.0~1.1) mmol:(75~85) mL；
The tin source is in terms of tin.
6. preparation method as claimed in claim 3, which is characterized in that the amount ratio of the sponge carbon and the mixed solution is
(1.2~5.6) g:(70~80) mL.
7. preparation method as claimed in claim 3, which is characterized in that the temperature of the hydro-thermal reaction is 110~130 DEG C, institute
The time for stating hydro-thermal reaction is 8~12h.
8. preparation method as claimed in claim 3, which is characterized in that the sintering carries out in protective atmosphere；
The temperature of the sintering is 450~650 DEG C, and heating rate is 1~2 DEG C/min, the soaking time of the sintering is 2~
5h。
9. preparation method as claimed in claim 3, which is characterized in that the preparation method of the sponge carbon the following steps are included:
Under an inert atmosphere, melamine sponge is subjected to high temperature cabonization, obtains sponge carbon；
The temperature of the high temperature cabonization is 750~850 DEG C, and heating rate is 4.5~5.5 DEG C/min, the guarantor of the high temperature cabonization
The warm time is 1~3 hour；
Before the sponge carbon is placed in the mixed solution, hydrophilic treated is carried out to sponge carbon.
10. anode material of lithium-ion battery of any of claims 1 or 2 or by the described in any item preparation sides of claim 3~9
Application of the anode material of lithium-ion battery that method is prepared in sodium-ion battery.
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