CN107968192B - Preparation method of titanium dioxide/germanium nanocomposite, lithium ion battery cathode and lithium ion battery - Google Patents
Preparation method of titanium dioxide/germanium nanocomposite, lithium ion battery cathode and lithium ion battery Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 79
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 42
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 178
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 89
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000011787 zinc oxide Substances 0.000 claims abstract description 34
- 239000006260 foam Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 238000002791 soaking Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- -1 titanium dioxide compound Chemical class 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000011592 zinc chloride Substances 0.000 claims description 9
- 235000005074 zinc chloride Nutrition 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 150000002290 germanium Chemical class 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 7
- GXMNGLIMQIPFEB-UHFFFAOYSA-N tetraethoxygermane Chemical compound CCO[Ge](OCC)(OCC)OCC GXMNGLIMQIPFEB-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 14
- 230000009467 reduction Effects 0.000 abstract description 5
- 230000001351 cycling effect Effects 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 description 18
- 239000002073 nanorod Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VRLRURDUSWOKRM-UHFFFAOYSA-N ethanol tetrachlorogermane Chemical compound CCO.Cl[Ge](Cl)(Cl)Cl VRLRURDUSWOKRM-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
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- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a titanium dioxide/germanium nano composite material using foamed nickel as a substrate, a lithium ion battery cathode and a lithium ion battery. The preparation method of the invention prepares the zinc oxide template by using low-price raw materials, and obtains the composite nano material of the hollow tube titanium dioxide and the nano germanium particles self-supported by the foam nickel through wrapping, template removal, compounding and reduction, and the product has high purity, is applied to the cathode material of the lithium ion battery, and has high energy density and good cycling stability.
Description
Technical Field
The invention relates to the technical field of inorganic nano materials, in particular to a preparation method of a titanium dioxide/germanium nano composite material using foamed nickel as a substrate, a lithium ion battery cathode and a lithium ion battery.
Background
The lithium ion battery has the advantages of high specific capacity, no pollution, wide working temperature range, no memory effect and the like, and is considered as a next-generation energy storage device capable of replacing traditional energy sources such as fossil fuel and the like. In recent years, the rapid development of portable electronic devices, electric tools and electric automobile technologies has made higher demands on the performance of lithium ion batteries, and thus, researches on new generation of lithium ion battery cathode materials with high specific capacity and long cycle life are stimulated.
Graphite is the most widely used negative electrode material at present, but only one lithium atom is allowed to be inserted into every six carbon atoms in the graphite, and the corresponding theoretical reversible capacity is only 372 mAh/g. Therefore, it is an urgent matter to research a negative electrode material having a high specific capacity and a high power density instead of a graphite negative electrode. Germanium is considered to be a very promising negative electrode material for lithium ion batteries due to its advantages of high theoretical capacity, rapid lithium ion diffusion rate and high electrical conductivity.
However, similar to silicon and tin, germanium negative electrode materials generate huge volume change (300%) during charge and discharge cycles, and as the cycle is prolonged, the huge deformation caused by expansion causes the crushing of electrode materials and the collapse of electrode conductive networks, so that the cycle capacity of the battery is severely attenuated, and the practical application of the high-capacity materials is greatly hindered.
Disclosure of Invention
In view of the defects in the prior art, the technical problem to be solved by the invention is to provide a preparation method of a titanium dioxide/germanium nanocomposite material using foamed nickel as a substrate, a lithium ion battery cathode and a lithium ion battery. The invention prepares the zinc oxide template by using low-price raw materials, and obtains the composite nano material of hollow tube titanium dioxide and nano granular germanium by wrapping, template removing, compounding and reducing. The invention provides a preparation method of a composite material, which has the advantages of simple process, high yield and low cost, aiming at the technical problems of improving the cycling stability of germanium as an electrode material and the like.
The technical scheme adopted by the invention is as follows:
a method for preparing a titanium dioxide/germanium nanocomposite material using foamed nickel as a substrate, comprising the steps of:
A. mixing a zinc salt solution with an alkali liquor to obtain a mixed solution, putting foamed nickel into the mixed solution to react to obtain foamed nickel with zinc oxide growing on the surface, washing and drying the foamed nickel with zinc oxide growing on the surface; the specific surface area of the foamed nickel was 0.9m2/g；
In the step A, the zinc salt is one or two of zinc chloride and zinc nitrate, and the concentration of a zinc salt solution is 0.4-0.6 mol/L, preferably 0.46-0.52 mol/L;
the alkali liquor is one or two of potassium hydroxide solution and sodium hydroxide solution, and the concentration of the alkali liquor is 3.5-4.6 mol/L, preferably 3.8-4.2 mol/L;
the reaction temperature in the step A is 40-80 ℃, and preferably 45-60 ℃; the reaction time is 4-12 hours, preferably 5-8 hours;
the step A is vacuum drying, and the temperature is 30-80 ℃; the drying time is 2-18 hours, preferably 2-6 hours;
B. soaking the foamed nickel with zinc oxide growing on the surface in titanium dioxide sol, taking out, drying and sintering to obtain foamed nickel with zinc oxide/titanium dioxide compound growing on the surface;
the titanium dioxide can be synthesized by a sol-gel method, and the specific method comprises the following steps: 10mL of butyl titanate was dissolved in 75mL of absolute ethanol, lmL acetylacetone was added as a hydrolysis inhibitor, and the mixture was mixed well. Weighing 25mL of absolute ethyl alcohol and lmL deionized water, uniformly mixing, slowly dropwise adding the mixture into the mixed solution under magnetic stirring, and continuously stirring for 30 minutes to obtain light yellow transparent titanium dioxide sol.
The soaking time in the step B is 10 seconds to 8 minutes, preferably 40 seconds to 2 minutes;
the drying in the step B is vacuum drying, the temperature is 35-85 ℃, the optimal temperature is 55-70 ℃, and the time is 1-20 hours, and the optimal time is 1-3 hours;
in the step B, the sintering temperature is 450-650 ℃, preferably 480-550 ℃, and the sintering time is 1-4 hours, preferably 1-2 hours;
C. soaking the foamed nickel with the zinc oxide/titanium dioxide compound growing on the surface in an acid solution, taking out, washing and drying to obtain foamed nickel with hollow tubular titanium dioxide growing on the surface;
c, acid in the step C is one or two of acetic acid and hydrochloric acid, and the concentration of the acid is 4-30%, preferably 5-10%;
the soaking time in the step C is 3-20 minutes, and preferably 3-8 minutes;
the drying is vacuum drying, the temperature is 35-75 ℃, and the optimal temperature is 55-65 ℃; the time is 1-6 hours, preferably 1-2 hours;
D. soaking the foamed nickel with the hollow tubular titanium dioxide growing on the surface in a germanium salt solution, taking out, drying, and calcining in a tubular furnace in a reducing atmosphere to obtain the foamed nickel with the titanium dioxide/germanium nanocomposite growing on the surface, namely the titanium dioxide/germanium nanocomposite taking the foamed nickel as a substrate.
In the step D, the germanium salt is one or two of germanium tetrachloride and tetraethoxy germanium, and the concentration of the germanium salt solution is 0.01-0.2 mol/L, preferably 0.01-0.05 mol/L;
the soaking time in the step D is 20 seconds to 4 hours, preferably 2 to 3 hours;
the drying in the step D is vacuum drying, the temperature is 40-75 ℃, and the optimal temperature is 55-65 ℃; the time is 1-5 hours, preferably 1-2 hours;
the calcination temperature in the step D is 550-750 ℃, and preferably 600-680 ℃; the calcination time is 3-10 hours, preferably 4-7 hours;
the reducing atmosphere in the step D is 5 percent of H2A mixed gas of/Ar;
a titanium dioxide/germanium nano composite material with foamed nickel as a substrate, which is prepared by the preparation method of the titanium dioxide/germanium nano composite material with foamed nickel as the substrate;
a lithium ion battery cathode is prepared by using a titanium dioxide/germanium nano composite material with foamed nickel as a substrate;
a lithium ion battery is made using a negative electrode made of a titanium dioxide/germanium nanocomposite comprising foamed nickel as a substrate.
According to the preparation method, the zinc oxide nanorod directly grows on the foamed nickel by a template method, the zinc oxide nanorod is washed, dried, wrapped and removed of the template to obtain the foamed nickel self-supporting three-dimensional hollow tubular titanium dioxide, and finally, compounding and reduction treatment are carried out to obtain the germanium nanoparticle-loaded nano composite material of the foamed nickel self-supporting titanium dioxide three-dimensional nanotube array.
Compared with the prior art, the invention has the following advantages:
(1) in the prepared composite material, germanium nanoparticles are uniformly loaded inside and outside the titanium dioxide hollow pipe;
(3) the prepared composite material has uniform nano-particle distribution and no agglomeration phenomenon;
(3) the prepared composite material has stable performance, is not easy to denature in air and is easy to store;
(4) the prepared composite material is used as a lithium ion battery cathode material and has larger specific capacity and better cycle performance;
(5) the preparation method is simple, the raw materials are easy to obtain, the cost is low, and batch production can be carried out.
Drawings
FIG. 1 is an SEM image of a foamed nickel free-standing titanium dioxide and germanium nanocomposite prepared in example 1.
FIG. 2 is an SEM image of a foamed nickel free-standing titanium dioxide and germanium nanocomposite prepared in example 2.
FIG. 3 is an SEM image of a composite material of foamed nickel self-supporting titanium dioxide and nano germanium prepared in example 3.
FIG. 4 is an SEM image of a composite material of foamed nickel self-supporting titanium dioxide and nano germanium prepared in example 4.
FIG. 5 is an SEM image of a composite material of foamed nickel self-supporting titanium dioxide and nano germanium prepared in example 5.
FIG. 6 is an XRD pattern of the foam nickel self-supporting titanium dioxide and nano germanium composite material prepared in example 3
FIG. 7 is a graph of the cycling stability test of the nickel foam self-supporting titanium dioxide and germanium nanocomposite prepared in example 3 as a negative electrode material of a lithium ion battery at a current density of 200 mA/g.
Detailed Description
Example 1
1) Respectively dissolving 1.19g of zinc nitrate and 1.44g of sodium hydroxide in 10ml of water, mixing the zinc chloride solution and the potassium hydroxide solution under magnetic stirring to obtain a mixed solution, putting the cleaned nickel foam into the mixed solution, reacting at the constant temperature of 40 ℃ for 10 hours to obtain the nickel foam with the zinc oxide nanorods growing on the surface, taking out, washing and collecting, and drying at the temperature of 40 ℃ for 12 hours in vacuum.
2) Preparing titanium dioxide sol: 10mL of butyl titanate was dissolved in 75mL of absolute ethanol, lmL acetylacetone was added as a hydrolysis inhibitor, and the mixture was mixed well. Weighing 25mL of absolute ethyl alcohol and lmL deionized water, uniformly mixing, slowly dropwise adding the mixture into the mixed solution under magnetic stirring, and continuously stirring for 30 minutes to obtain light yellow transparent titanium dioxide sol.
Soaking the foamed nickel with the zinc oxide nano-rods growing on the surface in 20ml of titanium dioxide sol for 50 seconds, taking out, vacuum-drying at 40 ℃ for 5 hours, and then sintering at 450 ℃ for 4 hours to obtain the foamed nickel with the zinc oxide/titanium dioxide compound growing on the surface.
3) Soaking the foamed nickel with the zinc oxide/titanium dioxide composite growing on the surface in acetic acid with the mass concentration of 3% for 3 minutes, taking out, washing, and vacuum drying at 45 ℃ for 6 hours to obtain the foamed nickel with hollow tubular titanium dioxide growing on the surface.
4) Soaking foamed nickel with hollow tubular titanium dioxide growing on the surface in 0.01mol/L germanium tetrachloride ethanol solution for 30 minutes, taking out, vacuum drying at 40 ℃ for 5 hours, and then reducing in a tubular furnace (H)2Reduction is carried out in the atmosphere of/Ar mixed gas, the volume ratio of hydrogen to argon is 5:95, namely 5 percent of H2Ar mixed gas) and calcining for 8 hours at 550 ℃ to obtain the foam nickel self-supporting titanium dioxide/germanium nanocomposite material, namely the titanium dioxide/germanium nanocomposite material taking the foam nickel as a substrate.
Example 2
1) Respectively dissolving 0.61g of zinc chloride and 2.13g of potassium hydroxide in 10ml of water, mixing the zinc chloride solution and the potassium hydroxide solution under magnetic stirring to obtain a mixed solution, putting the cleaned nickel foam into the mixed solution, reacting at a constant temperature of 45 ℃ for 8 hours to obtain the nickel foam with the zinc oxide nanorods growing on the surface, taking out, washing and collecting, and drying in vacuum at 45 ℃ for 9 hours.
2) The titania sol was prepared in the same manner as in example 1. Soaking the foamed nickel with the zinc oxide nano-rods growing on the surface in 30ml of titanium dioxide sol for 2 minutes, taking out, vacuum-drying at 45 ℃ for 3 hours, and then sintering at 500 ℃ for 2 hours to obtain the foamed nickel with the zinc oxide/titanium dioxide compound growing on the surface.
3) Soaking the foamed nickel with the zinc oxide/titanium dioxide compound growing on the surface in 4 mass percent hydrochloric acid for 5 minutes, taking out, washing, and vacuum drying at 60 ℃ for 2 hours to obtain the foamed nickel with hollow tubular titanium dioxide growing on the surface.
4) Soaking foamed nickel with hollow tubular titanium dioxide growing on the surface in 0.01mol/L tetraethoxy germanium ethanol solution for 2 hours, taking out, vacuum drying at 55 ℃ for 2 hours, and then reducing in a tubular furnace (H)2Reduction is carried out in the atmosphere of/Ar mixed gas, the volume ratio of hydrogen to argon is 5:95, namely 5 percent of H2Ar mixed gas) and calcining for 6 hours at 600 ℃ to obtain the foam nickel self-supporting titanium dioxide/germanium nanocomposite material, namely the titanium dioxide/germanium nanocomposite material taking the foam nickel as a substrate.
Example 3
1) Respectively dissolving 1.48g of zinc nitrate and 2.24g of potassium hydroxide in 10ml of water, mixing the zinc chloride solution and the potassium hydroxide solution under magnetic stirring to obtain a mixed solution, putting the cleaned nickel foam into the mixed solution, reacting at a constant temperature of 60 ℃ for 4 hours to obtain the nickel foam with the zinc oxide nano-rods growing on the surface, taking out, washing and collecting, and drying in vacuum at 50 ℃ for 4 hours
2) The titania sol was prepared in the same manner as in example 1. Soaking the foamed nickel with the zinc oxide nano-rods growing on the surface in 35ml of titanium dioxide sol for 1 minute, taking out, vacuum-drying at 55 ℃ for 2 hours, and then sintering at 500 ℃ for 2 hours to obtain the foamed nickel with the zinc oxide/titanium dioxide compound growing on the surface.
3) Soaking the foamed nickel with the zinc oxide/titanium dioxide composite growing on the surface in acetic acid with the mass concentration of 5% for 5 minutes, taking out, washing, and vacuum drying at 60 ℃ for 2 hours to obtain the foamed nickel with the hollow tubular titanium dioxide growing on the surface.
4) Soaking foamed nickel with hollow tubular titanium dioxide growing on the surface in 0.05mol/L germanium tetrachloride ethanol solution for 3 hours, taking out, vacuum drying at 60 ℃ for 1 hour, and then putting into a tubular furnace for reduction (H)2Reduction is carried out in the atmosphere of/Ar mixed gas, the volume ratio of hydrogen to argon is 5:95, namely 5 percent of H2Mixed gas of/Ar) and calcining for 4 hours at 650 ℃ to obtain the foam nickel self-supporting titanium dioxide/germanium nanocomposite material, namely the titanium dioxide/germanium nanocomposite material taking the foam nickel as a substrate.
Example 4
1) Respectively dissolving 0.75g of zinc chloride and 1.68g of sodium hydroxide in 10ml of water, mixing the zinc chloride solution and the potassium hydroxide solution under magnetic stirring to obtain a mixed solution, putting the cleaned nickel foam into the mixed solution, reacting at a constant temperature of 50 ℃ for 6 hours to obtain the nickel foam with zinc oxide nanorods growing on the surface, taking out, washing and collecting, and drying in vacuum at 60 ℃ for 2 hours
2) The titania sol was prepared in the same manner as in example 1. Soaking the foamed nickel with the zinc oxide nano-rods growing on the surface in 45ml of titanium dioxide sol for 5 minutes, taking out, drying in vacuum at 60 ℃ for 1 hour, and then sintering at 550 ℃ for 1 hour to obtain the foamed nickel with the zinc oxide/titanium dioxide compound growing on the surface.
3) Soaking the foamed nickel with the zinc oxide/titanium dioxide compound growing on the surface in 10 mass percent hydrochloric acid for 8 minutes, taking out, washing, and vacuum drying at 65 ℃ for 1 hour to obtain the foamed nickel with hollow tubular titanium dioxide growing on the surface.
4) Soaking foamed nickel with hollow tubular titanium dioxide growing on the surface in 0.1mol/L tetraethoxy germanium ethanol solution for 2.5 hours, taking out, vacuum drying at 65 ℃ for 1 hour, and then putting into a tubular furnace for reduction (H)2Reduction is carried out in the atmosphere of/Ar mixed gas, the volume ratio of hydrogen to argon is 5:95, namely 5 percent of H2Ar mixed gas) at 650 ℃ for 5 hours to obtain the foam nickel self-supporting titanium dioxide/germanium nano composite material, namely the foam nickel is used as the baseA titanium dioxide/germanium nanocomposite.
Example 5
1) Respectively dissolving 1.78g of zinc nitrate and 2.52g of potassium hydroxide in 10ml of water, mixing the zinc chloride solution and the potassium hydroxide solution under magnetic stirring to obtain a mixed solution, putting the cleaned nickel foam into the mixed solution, reacting at the constant temperature of 70 ℃ for 3 hours to obtain the nickel foam with the zinc oxide nano-rods growing on the surface, taking out, washing and collecting, and drying in vacuum at the temperature of 70 ℃ for 1 hour
2) The titania sol was prepared in the same manner as in example 1. Soaking the foamed nickel with the zinc oxide nano-rods growing on the surface in 60ml of titanium dioxide sol for 1 minute, taking out, vacuum-drying at 75 ℃ for 40 minutes, and then sintering at 600 ℃ for 1 hour to obtain the foamed nickel with the zinc oxide/titanium dioxide compound growing on the surface.
3) Soaking the foamed nickel with the zinc oxide/titanium dioxide composite growing on the surface in acetic acid with the mass concentration of 20% for 10 minutes, taking out, washing, and vacuum drying at 75 ℃ for 1 hour to obtain the foamed nickel with hollow tubular titanium dioxide growing on the surface.
4) Soaking the foamed nickel with the hollow tubular titanium dioxide growing on the surface in 0.2mol/L germanium tetrachloride ethanol solution for 4 hours, taking out, vacuum-drying at 70 ℃ for 45 minutes, and then putting into a tubular furnace for reduction (H)2Reduction is carried out in the atmosphere of/Ar mixed gas, the volume ratio of hydrogen to argon is 5:95, namely 5 percent of H2Ar mixed gas) and calcining for 4 hours at 700 ℃ to obtain the foam nickel self-supporting titanium dioxide/germanium nanocomposite material, namely the titanium dioxide/germanium nanocomposite material taking the foam nickel as a substrate.
The final product obtained in the example 3 uses the titanium dioxide/germanium nano composite material with the foamed nickel as the substrate as the negative electrode material of the lithium ion battery, a mechanical cutting machine is adopted to cut an electrode slice, the electrode slice is pressed into an electrode slice with the diameter of 0.1 mu m by a pressing machine, a lithium slice is used as a counter electrode, and the electrolyte is 1mol/L LiPF sold in the market6And the charge and discharge performance of the/EC + DMC solution is tested by using a battery tester, and the result of the cycle stability test of the obtained product as the lithium ion battery negative electrode material under the current density of 200mA/g is shown in figure 7. As can be seen from fig. 7, of the batteryThe cycling stability is good, and the battery capacity is still stable at 653mAh/g after 100 cycles.
Claims (18)
1. A method for preparing titanium dioxide/germanium nano composite material using foam nickel as a substrate comprises the following steps:
A. mixing a zinc salt solution with an alkali liquor to obtain a mixed solution, putting the foamed nickel into the mixed solution to react to obtain foamed nickel with zinc oxide growing on the surface, washing the foamed nickel with zinc oxide growing on the surface, and drying;
B. soaking the foamed nickel with zinc oxide growing on the surface in titanium dioxide sol, taking out, drying and sintering to obtain foamed nickel with zinc oxide/titanium dioxide compound growing on the surface;
C. soaking the foamed nickel with the zinc oxide/titanium dioxide compound growing on the surface in an acid solution, taking out, washing and drying to obtain foamed nickel with hollow tubular titanium dioxide growing on the surface;
D. soaking the foamed nickel with the hollow tubular titanium dioxide growing on the surface in a germanium salt solution, taking out, drying, and calcining in a tubular furnace in a reducing atmosphere to obtain the foamed nickel with the titanium dioxide/germanium nanocomposite growing on the surface, namely the titanium dioxide/germanium nanocomposite taking the foamed nickel as a substrate.
2. The method of claim 1, wherein: in the step A, zinc salt is one or two of zinc chloride and zinc nitrate, and the concentration of a zinc salt solution is 0.4-0.6 mol/L;
the alkali liquor is one or two of potassium hydroxide solution and sodium hydroxide solution, and the concentration of the alkali liquor is 3.5-4.6 mol/L.
3. The method of claim 2, wherein: the concentration of the zinc salt solution is 0.46-0.52 mol/L; the concentration of the alkali liquor is 3.8-4.2 mol/L.
4. The method of claim 1, wherein: the reaction temperature in the step A is 40-80 ℃; the reaction time is 4-12 hours.
5. The method of claim 4, wherein: the reaction temperature in the step A is 45-60 ℃; the reaction time is 5-8 hours.
6. The method of claim 1, wherein: the soaking time in the step B is 10 seconds to 8 minutes; the soaking time in the step C is 3-20 minutes; and D, soaking for 20 seconds to 4 hours.
7. The method of claim 6, wherein: the soaking time in the step B is 40 seconds to 2 minutes; the soaking time in the step C is 3-8 minutes; and D, soaking for 2-3 hours.
8. The method of claim 1, wherein: and in the step B, the sintering temperature is 450-650 ℃, and the sintering time is 1-4 hours.
9. The method of claim 1, wherein: and in the step B, the sintering temperature is 480-550 ℃, and the sintering time is 1-2 hours.
10. The method of claim 1, wherein: and C, in the step C, the acid is one or two of acetic acid and hydrochloric acid, and the mass percentage concentration of the acid is 4-30%.
11. The method of claim 10, wherein: the mass percentage concentration of the acid is 5-10%.
12. The method of claim 1, wherein: and D, the germanium salt in the step D is one or two of germanium tetrachloride and tetraethoxy germanium, and the concentration of the germanium salt solution is 0.01-0.2 mol/L.
13. The method of claim 1, wherein: the concentration of the germanium salt solution is 0.01-0.05 mol/L.
14. The method of claim 1, wherein: the calcining temperature in the step D is 550-750 ℃; the calcination time is 3-10 hours.
15. The method of claim 14, wherein: the calcining temperature in the step D is 600-680 ℃; the calcination time is 4-7 hours.
16. The method of claim 1, wherein: the reducing atmosphere in the step D is 5 percent of H2and/Ar mixed gas.
17. A negative electrode of a lithium ion battery is made of a titanium dioxide/germanium nano composite material using foamed nickel as a substrate.
18. A lithium ion battery is made using a negative electrode made of a titanium dioxide/germanium nanocomposite material including a foamed nickel as a substrate.
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| CN103943836A (en) * | 2014-04-01 | 2014-07-23 | 太原理工大学 | Hollow germanium nanotube array electrode of lithium ion battery anode material and preparation method of array electrode |
| CN105355925A (en) * | 2015-10-30 | 2016-02-24 | 上海科技大学 | Preparation method of three-dimensional ordered nickel skeleton germanium-loaded lithium battery negative electrode material |
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| CN103943836A (en) * | 2014-04-01 | 2014-07-23 | 太原理工大学 | Hollow germanium nanotube array electrode of lithium ion battery anode material and preparation method of array electrode |
| CN105355925A (en) * | 2015-10-30 | 2016-02-24 | 上海科技大学 | Preparation method of three-dimensional ordered nickel skeleton germanium-loaded lithium battery negative electrode material |
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| Title |
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| Titanium Dioxide/Germanium Core–Shell Nanorod Arrays;Shan Fang et.al;《Particle & Particle Systerms Characterization》;20140926;全文 * |
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