CN117712295A - High-energy-density, long-cycle and high-first-efficiency lithium-free battery cathode and preparation method thereof - Google Patents
High-energy-density, long-cycle and high-first-efficiency lithium-free battery cathode and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 21
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- 229910045601 alloy Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 10
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 239000006183 anode active material Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
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- 239000000126 substance Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 4
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000006256 anode slurry Substances 0.000 claims description 2
- 239000011889 copper foil Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 239000002109 single walled nanotube Substances 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
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- 238000006138 lithiation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
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- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
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- 238000009831 deintercalation Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
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- 230000007704 transition Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a high-energy density, long-cycle and high-first-efficiency lithium-free battery cathode and a preparation method thereof, wherein a low-temperature solvothermal method is adopted to prepare a molybdenum trioxide hybrid which is used as a precursor and is mixed with tin powder for thermal reduction, a Sn-Mo alloy cathode active material with a regular structure is constructed, the cathode active material, a conductive agent, a binder and a dispersing agent are mixed according to a certain proportion to form slurry, the mixed slurry is coated on a proper current collector through coating equipment and is dried, and finally the lithium-free battery cathode with a Sn-Mo alloy nano layer is obtained. The negative electrode alloying structure of the invention accelerates the rapid diffusion rate of lithium ions and improves the multiplying power performance and long-cycle stability of the material. The invention has simple process and obviously and reliably improved performance, and the battery cathode material has higher energy density and excellent first-time efficiency. The Sn-Mo alloy composite layer is used as a negative electrode, which is favorable for uniformly depositing lithium on the current collector, thereby improving the performance of the all-solid-state battery.
Description
Technical Field
The invention belongs to the technical field of material synthesis, relates to a lithium-free negative electrode of a lithium ion solid-state battery and a preparation method thereof, and particularly relates to a high-energy-density, long-cycle and high-first-efficiency negative electrode of a lithium-free battery and a preparation method thereof.
Background
In modern society, the wide application of portable electronic devices and electric vehicles has driven the rapid development of rechargeable Lithium Ion Batteries (LIBs). However, there are many problems with the alkali metal lithium used by conventional LIBs as the negative electrode. Lithium metal has a very high theoretical specific capacity, but during discharge and charge, lithium ions react with the electrode material to form a Solid Electrolyte Interface (SEI), resulting in loss of available lithium, reducing the cycle life of the battery. In addition, there are safety problems during storage and use due to the high activity of lithium metal. These problems are significant challenges for current lithium metal batteries, whether in terms of structural design, synthetic methods, and even stability. In addition, in a lithium ion battery, lithium metal is used as a negative electrode, and the problem of 'lithium intercalation' is encountered, namely, the volume expansion and shrinkage caused by intercalation and deintercalation of lithium ions in a negative electrode material in the charge and discharge process, so that the cracking and fracture of the electrode material are caused, and the service life and performance of the battery are influenced.
In view of these problems, researchers have begun to find battery cathodes that replace lithium metal, and no lithium battery cathodes are a good choice. The cathode of the lithium-free battery has higher chemical stability, is not easy to cause the problem of lithium intercalation, is safer and is likely to improve the cycle performance of the battery. While lithium-free anode materials are superior to conventional lithium metal anode materials in many respects, they still present some problems and challenges: 1. electrochemical performance differences: many lithium-free anode materials have a large difference in electrochemical properties compared to lithium metal, such as energy density, rate capability, and cycle life, which limits their application in the field of high-performance batteries; 2. volume expansion and fracture: although lithium-free anode materials can reduce lithium intercalation problems, they can still undergo volume expansion and contraction during charge and discharge. This can cause cracking and breakage of the material, affecting the stability and life of the battery. 3. Manufacturing and cost: the development of new lithium-free anode materials and the design of suitable battery structures requires solutions to some manufacturing technical difficulties and may lead to increased costs. In view of the challenges, the lithium-free anode material developed by the patent meets the requirements of various battery applications on high performance, safety and reliability by optimizing the material performance, improving the stability of an electrochemical interface, improving the charge and discharge efficiency, reducing the cost and the like.
Disclosure of Invention
The invention aims to provide a high-energy-density, long-cycle and high-first-efficiency lithium-free battery cathode and a preparation method thereof, which are used for effectively solving the problems of unstable electrochemical interface of the lithium-free cathode, low first-efficiency of charge and discharge, low energy density, lithium intercalation and the like.
The invention adopts a low-temperature solvothermal method to prepare linear molybdenum trioxide (MoO) 3 ) The hybrid is used as a precursor and mixed with commercial tin powder for thermal reduction, so that the Sn-Mo alloy anode material with a regular structure is successfully constructed. During lithiation, the Sn-Mo alloy may be converted to Mo nanoparticles, which may help alleviate the transition fromPressure generated by great change of Sn metal volume and prevent coarsening of Sn particles to reduce Li + And improves the lithiation rate. In addition, the SnMo layer can provide a richer electron conduction channel to enhance high electron conductivity. This improved construction method and material demonstrate excellent performance and high initial efficiency in lithium ion battery applications. And mixing the prepared material with a conductive agent, a binder and a dispersing agent according to a certain proportion to form slurry, coating the mixed slurry on a proper current collector through coating equipment, and drying to finally obtain the lithium-free battery anode with the Sn-Mo alloy nano layer. The Sn-Mo nano composite layer is used as an effective additive layer suitable for all-solid-state batteries to replace pure lithium metal as a negative electrode, and can obviously improve the uniform deposition and stable cycle performance of lithium on a current collector, thereby improving the safety and the cycle life of the battery.
The preparation method comprises the following specific steps:
dissolving a proper amount of molybdenum source compound in a certain amount of solvent, stirring, and adding a certain amount of amine component substances into the solution after the solution is completely dissolved. Then, hydrochloric acid of different concentrations was slowly added thereto, and white precipitate was generated at a certain pH value. And the following steps are carried out: stirring and heating at 50-90deg.C for 1-2 hr in oil bath, filtering and washing, and drying at 60-80deg.C in vacuum oven for 6-12 hr to obtain MoO 3 EDA hybrid compounds.
Grinding and mixing a proper amount of the product and tin powder according to a certain mass ratio, and calcining the ground product for 2-8 hours at 550-1050 ℃ under an inert atmosphere at a heating rate of 2-10 ℃/min to obtain the Sn-Mo alloy anode active material.
Mixing the Sn-Mo alloy anode active material, the conductive agent and the binder in the second step according to a certain weight ratio, slowly adding the dispersing agent into the mixture under constant stirring, preparing anode slurry by using a slurry mixer, then coating the slurry on a metal current collector by using a coating machine, and drying the obtained electrode at the temperature of between 60 and 80 ℃ for 6 to 12 hours. The active substance mass of the prepared Sn-Mo nano composite layer is about 1-2 mg.
Preferably, the molybdenum source compound in the preparation method is one or a mixture of two of ammonium molybdate tetrahydrate and sodium molybdate.
Preferably, the amine component substance in the preparation method is one or a mixture of two of ethylenediamine and aniline.
Preferably, the solvent in the preparation method is one or more of deionized water, ethanol and methanol.
Preferably, the hydrochloric acid concentration in the preparation method is 1-3M.
Preferably, the pH of the above preparation is in the range of about 4 to about 6.5.
Preferably, in the second step, moO 3 The mass ratio of EDA hybrid compound to tin powder is 1:1-1:3.
Preferably, the inert atmosphere in the preparation method is argon or hydrogen-argon mixed gas.
Preferably, in the third step, the weight ratio of the Sn-Mo alloy anode active material, the conductive agent and the binder is 7:2:1 or 8:1:1.
preferably, the conductive agent in the third step is Super P conductive agent, single-walled carbon nanotube and acetylene black; the binder is polyvinylidene fluoride (PVDF) and sodium carboxymethylcellulose (CMC); the dispersing agent is ultrapure water or N-methyl pyrrolidone (NMP); the metal current collector is copper foil, stainless steel foil or titanium foil.
The invention has the following beneficial effects:
(1) The invention provides a high-energy-density, long-cycle and high-first-efficiency lithium-free battery cathode and a preparation method thereof. The unique alloying structure ensures the stability of the composite material structure, enhances the reaction kinetics of the built-in electric field effect and accelerates the rapid diffusion rate of lithium ions, thereby effectively improving the multiplying power performance and the long-cycle stability of the material;
(2) The invention has simple process, obviously and reliably improved performance, and the battery anode material prepared by using the common molybdenum source and tin powder has higher energy density and excellent first efficiency, and reduces the cost. The Sn-Mo alloy composite layer is introduced to replace pure lithium metal as a negative electrode, so that lithium is uniformly deposited on the current collector, and the performance of the all-solid-state battery is improved.
Drawings
FIG. 1 is an XRD pattern of a high energy density, long cycle, high first efficiency lithium-free battery negative electrode prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of a high energy density, long cycle, high first efficiency lithium-free battery negative electrode prepared in example 2 of the present invention;
FIG. 3 is an XRD pattern of a high energy density, long cycle, high first efficiency lithium-free battery negative electrode prepared in accordance with the comparative example of the present invention;
FIG. 4 is a charge-discharge curve graph of the high energy density, long cycle, high first efficiency lithium-free battery anode prepared in example 1 of the present invention with respect to the first efficiency (at 1A g -1 At current density);
FIG. 5 is a charge-discharge curve graph of the high energy density, long cycle, high first efficiency lithium-free battery anode prepared in example 2 of the present invention with respect to the first efficiency (at 1A g -1 At current density);
FIG. 6 is a charge-discharge graph of the high energy density, long cycle, high first efficiency lithium-free battery negative electrode prepared according to the comparative example of the present invention with respect to the first efficiency (at 1A g -1 At current density);
FIG. 7 shows the high energy density, long cycle, high initial efficiency lithium-free battery negative electrode at 1A g prepared in the examples and comparative examples of the present invention -1 Long cycle performance plot at current density (1000 cycles).
Detailed Description
The following description of the present invention is provided with reference to the accompanying drawings, but is not limited to the following description, and any modifications or equivalent substitutions of the present invention should be included in the scope of the present invention without departing from the spirit and scope of the present invention.
Example 1
1. 2.48. 2.48 g ammonium molybdate tetrahydrate was dissolved in 30 mL ultrapure water and stirred, and 1.6. 1.6 g ethylenediamine was added thereto after complete dissolution. Then, 1M hydrochloric acid solution was slowly added thereto at ph=6A white precipitate was produced. And the following steps are carried out: stirring and heating at 50deg.C for 2 hr in oil bath, filtering and washing the heated product, and drying at 60deg.C in vacuum oven for 12 hr to obtain MoO 3 EDA hybrid compounds.
2. Grinding and mixing a proper amount of the product and commercial tin powder according to a certain mass ratio. The milled product was calcined at 1050 c for 8 hours under an inert atmosphere at a heating rate of 5 c/min to give the final product.
3. Mixing the product obtained in the step two with Super P and PVDF according to a weight ratio of 8:1:1, NMP was slowly added to the mixture with constant stirring, and a negative electrode slurry was prepared using an AR-100 type mixer of Thinky Corporation, followed by coating the slurry on a metal current collector using a coater, and drying in air at 80 ℃ for 20 minutes. The resulting electrode was further dried under vacuum at 100℃for 12 hours.
Example 2
1. 2.48. 2.48 g ammonium molybdate tetrahydrate was dissolved in 30 mL ultrapure water and stirred, and 1.6. 1.6 g ethylenediamine was added thereto after complete dissolution. Then, 1M hydrochloric acid solution was slowly added thereto, resulting in white precipitation at ph=6. And the following steps are carried out: stirring and heating at 50deg.C for 2 hr in oil bath, filtering and washing the heated product, and drying at 60deg.C in vacuum oven for 12 hr to obtain MoO 3 EDA hybrid compounds.
2. Grinding and mixing a proper amount of the product and commercial tin powder according to a certain mass ratio. The milled product was calcined at 550 c for 8 hours under an inert atmosphere at a heating rate of 5 c/min to obtain the final product.
3. Mixing the product obtained in the step two with Super P and PVDF according to a weight ratio of 8:1:1, NMP was slowly added to the mixture with constant stirring, and a negative electrode slurry was prepared using an AR-100 type mixer of Thinky Corporation, followed by coating the slurry on a metal current collector using a coater, and drying in air at 80 ℃ for 20 minutes. The resulting electrode was further dried under vacuum at 100℃for 12 hours.
Comparative example:
1. sodium molybdate of 2.48. 2.48 g was dissolved in ultrapure water of 30. 30 mL and stirred, and aniline of 1.6. 1.6 g was added thereto after complete dissolution. Then, 1M hydrochloric acid solution was slowly added thereto, resulting in white precipitation at ph=6. And the following steps are carried out: stirring and heating at 50deg.C for 2 hr in oil bath, filtering and washing the heated product, and drying at 60deg.C in vacuum oven for 12 hr to obtain MoO 3 EDA hybrid compounds.
2. Grinding and mixing a proper amount of the product and commercial tin powder according to a certain mass ratio. The milled product was calcined at 300 c for 8 hours under an inert atmosphere at a heating rate of 5 c/min to obtain the final product.
3. Mixing the product obtained in the step II of the comparative example with Super P and CMC according to the weight ratio of 7:2:1, ultra-pure water was slowly added to the mixture with constant stirring, and a negative electrode slurry was prepared using an AR-100 type mixer of Thinky Corporation, followed by coating the slurry on a metal current collector using a coater, and drying in air at 80 ℃ for 20 minutes. The resulting electrode was further dried under vacuum at 100℃for 12 hours.
XRD tests of the high energy density, long cycle, high first efficiency lithium-free battery cathodes prepared in example 1, example 2 and comparative example are shown in FIG. 1, FIG. 2 and FIG. 3, wherein the negative electrode materials prepared in comparative example have obvious peak shapes of elemental Sn and elemental Mo, and molybdenum trioxide is subjected to phase transformation at the temperature to generate elemental Sn, but no Sn-Mo alloy is possible to generate. As the temperature increases to 550 ℃, there is a peak shape of the amorphous sn—mo alloy (example 2). When the reaction temperature was further increased to 1050 ℃, not only diffraction peaks of Sn and Mo but also new peak shapes appeared in the system, indicating the formation of Sn-Mo alloy materials with better crystallinity and high purity (example 1).
The first charge-discharge efficiency pairs of the anode materials prepared in examples 1 and 2 and the comparative samples prepared in comparative examples are shown in fig. 4, fig. 5 and fig. 6. By comparison of the three at a current density of 1A/g, the first charge-discharge efficiency of comparative example and example 2 was only 73.8%, whereas the first charge-discharge efficiency of example 1 was 91.4%, and the specific capacity of the first charge in the examples was higher than that of the comparative example at a low voltage (0.5V), which is also the main reason why the first effect was higher than that of the comparative example. And 1000 cycles of the three at the current are shown in fig. 7, after 1000 cycles, the capacity of the example 1 and the capacity of the comparative example are almost the same, but the capacity of the example 1 and the capacity of the comparative example both show a high specific capacity of 300 mAh/g after the cycle, and the number of required activation cycles of the example 1 is less than 30 (200 times of comparative example) compared with the comparative example, which proves the superiority of the material, whereas the specific capacity of the example 2 is about 600 mAh/g, but the initial efficiency is lower, and the experimental parameters in the example 1 are more in accordance with the application range of the patent by comprehensive consideration.
Claims (10)
1. The preparation method of the lithium-free battery cathode with high energy density, long cycle and high first efficiency is characterized by comprising the following process steps:
(1) Dissolving a proper amount of molybdenum source compound in a solvent, stirring, and adding a certain amount of amine component substances into the solution after the solution is completely dissolved; then, hydrochloric acid of different concentrations was slowly added thereto to produce white precipitate at a certain pH value, and the following steps were performed: stirring and heating at 50-90deg.C for 2 hr in oil bath, filtering and washing, and drying at 60-80deg.C in vacuum oven for 6-12 hr to obtain MoO 3 -EDA hybrid compounds;
(2) Mixing the MoO with the above 3 Grinding and mixing EDA hybrid compound and tin powder according to a certain mass ratio; the grinded product is calcined for 2 to 8 hours at 550 to 1050 ℃ at a heating rate of 2 to 10 ℃/min under inert atmosphere, and the Sn-Mo alloy anode active material is obtained;
(3) Mixing the Sn-Mo alloy anode active material, the conductive agent and the binder in the step (2) according to a certain weight ratio, slowly adding a dispersing agent into the mixture under constant stirring, preparing anode slurry after mixing, then coating the slurry on a metal current collector by using a coating machine, and further drying the obtained electrode at 60-80 ℃ under vacuum for 12 hours to obtain the lithium-free battery anode.
2. The method for preparing the high-energy-density, long-cycle and high-first-efficiency lithium-free battery cathode according to claim 1, wherein the molybdenum source compound is one or a mixture of two of ammonium molybdate tetrahydrate and sodium molybdate.
3. The method for preparing the lithium-free battery cathode with high energy density, long cycle and high initial efficiency according to claim 1, wherein the amine component substance is one or a mixture of two of ethylenediamine and aniline.
4. The method for preparing the lithium-free battery anode with high energy density, long cycle and high initial efficiency according to claim 1, wherein the solvent is one or more of deionized water, ethanol and methanol.
5. The method for preparing the negative electrode of the high-energy-density, long-cycle and high-initial-efficiency lithium-free battery according to claim 1, wherein the concentration of hydrochloric acid is 1-3M.
6. The method for preparing the negative electrode of the lithium-free battery with high energy density, long cycle and high initial efficiency according to claim 1, wherein the pH value interval of the preparation method is 4-6.5.
7. The method for preparing a negative electrode of a high energy density, long-cycle, high-first-efficiency lithium-free battery according to claim 1, wherein in the step (2), moO is added 3 The mass ratio of EDA hybrid compound to tin powder is 1:1-1:3.
8. The method for preparing the negative electrode of the lithium-free battery with high energy density, long cycle and high initial efficiency according to claim 1, wherein the weight ratio of the active material of the Sn-Mo alloy negative electrode, the conductive agent and the binder in the step (3) is 7:2:1 or 8:1:1.
9. the method for preparing the negative electrode of the lithium-free battery with high energy density, long cycle and high initial efficiency according to claim 1, wherein the conductive agent in the step (3) is one of Super P conductive agent, single-walled carbon nanotube and acetylene black; the binder is one of polyvinylidene fluoride and sodium carboxymethyl cellulose; the dispersing agent is one of ultrapure water and N-methyl pyrrolidone; the metal current collector is one of copper foil, stainless steel foil and titanium foil.
10. A high energy density, long cycle, high first efficiency lithium free battery negative electrode made by the method of any one of claims 1-9, wherein the lithium free battery negative electrode has a Sn-Mo alloy nanolayer active material.
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