CN116581282A - Alloyed negative electrode material, preparation method and application thereof - Google Patents
Alloyed negative electrode material, preparation method and application thereof Download PDFInfo
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- CN116581282A CN116581282A CN202310857202.7A CN202310857202A CN116581282A CN 116581282 A CN116581282 A CN 116581282A CN 202310857202 A CN202310857202 A CN 202310857202A CN 116581282 A CN116581282 A CN 116581282A
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 48
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 48
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011148 porous material Substances 0.000 claims abstract description 35
- 238000005275 alloying Methods 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000012792 core layer Substances 0.000 claims abstract description 11
- 239000011247 coating layer Substances 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 238000005253 cladding Methods 0.000 claims abstract description 8
- 239000010410 layer Substances 0.000 claims abstract description 7
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- JDTCYQUMKGXSMX-UHFFFAOYSA-N dimethyl(methylsilyl)silane Chemical compound C[SiH2][SiH](C)C JDTCYQUMKGXSMX-UHFFFAOYSA-N 0.000 claims description 3
- UCMVNBCLTOOHMN-UHFFFAOYSA-N dimethyl(silyl)silane Chemical compound C[SiH](C)[SiH3] UCMVNBCLTOOHMN-UHFFFAOYSA-N 0.000 claims description 3
- RUIGDFHKELAHJL-UHFFFAOYSA-N dimethylgermane Chemical compound C[GeH2]C RUIGDFHKELAHJL-UHFFFAOYSA-N 0.000 claims description 3
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 claims description 3
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 3
- KCWYOFZQRFCIIE-UHFFFAOYSA-N ethylsilane Chemical compound CC[SiH3] KCWYOFZQRFCIIE-UHFFFAOYSA-N 0.000 claims description 3
- 239000010408 film Substances 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- IQCYANORSDPPDT-UHFFFAOYSA-N methyl(silyl)silane Chemical compound C[SiH2][SiH3] IQCYANORSDPPDT-UHFFFAOYSA-N 0.000 claims description 3
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 claims description 3
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- 239000002121 nanofiber Substances 0.000 claims description 3
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- VIPCDVWYAADTGR-UHFFFAOYSA-N trimethyl(methylsilyl)silane Chemical compound C[SiH2][Si](C)(C)C VIPCDVWYAADTGR-UHFFFAOYSA-N 0.000 claims description 3
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002135 nanosheet Substances 0.000 claims 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
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- 238000009826 distribution Methods 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
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- 239000011366 tin-based material Substances 0.000 description 3
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- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
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- AXQKVSDUCKWEKE-UHFFFAOYSA-N [C].[Ge].[Si] Chemical compound [C].[Ge].[Si] AXQKVSDUCKWEKE-UHFFFAOYSA-N 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/12—Metallic powder containing non-metallic particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides an alloying negative electrode material, a preparation method and application thereof, and particularly relates to the technical field of lithium battery negative electrode materials. The alloyed negative electrode material comprises an alloyed composite material as a core layer; and a carbon cladding layer surrounding the core layer; the alloying composite material comprises an inorganic porous material and a germanium simple substance positioned in pore channels of the inorganic porous material; the elemental germanium accounts for 10wt.% to 90wt.% of the alloyed negative electrode material. The alloying anode material provided by the invention has high theoretical capacity (1600 mAh/g) and high diffusion coefficient (100 cm) 2 S) and high conductivity (2.17 s/m) germaniumThe inorganic porous material is used in the anode material to provide space for contraction and expansion of germanium, and the carbon coating layer improves the stability of the core layer material, and the first effect and the reversible capacity of the anode material are cooperatively improved, so that the cycle stability of the anode material is greatly improved.
Description
Technical Field
The invention relates to the technical field of lithium battery anode materials, in particular to an alloying anode material and a preparation method and application thereof.
Background
In recent years, negative electrode materials such as silicon-based materials, tin-based materials, titanium-based materials, transition metal oxides, and various composite negative electrode materials having high specific capacities have been developed gradually, and have become an important research direction for improving the energy density of lithium ion batteries.
The silicon-based negative electrode has the defects of large volume change, poor circulation and low initial efficiency in the charge and discharge process, and the commercial application of the silicon-based negative electrode is limited. The tin-based material, the titanium-based material and the transition metal oxide have the defect of small theoretical capacity in the charge and discharge process, so that the application cost of the tin-based material, the titanium-based material and the transition metal oxide in the lithium battery is increased.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide an alloying anode material, which aims to solve the technical problem that the anode material in the prior art cannot simultaneously consider capacity, cycle performance and service life.
The second purpose of the invention is to provide a preparation method of the alloyed negative electrode material.
The invention further aims to provide an application of the alloyed negative electrode material in a negative electrode material of a lithium battery.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the first aspect of the present invention provides an alloyed negative electrode material comprising an alloyed composite material as a core layer; and a carbon cladding layer surrounding the core layer;
the alloying composite material comprises an inorganic porous material and a germanium simple substance positioned in pore channels of the inorganic porous material;
wherein the inorganic porous material comprises one of porous ceramics, porous carbon materials, porous silica materials and molecular sieves;
the elemental germanium accounts for 1wt.% to 90wt.% of the alloyed negative electrode material.
Further, the thickness of the carbon coating layer is 1nm-20nm.
The porous ceramic material includes at least one of porous alumina, porous zirconia, porous magnesia, and porous beryllium oxide.
Further, the porous material also comprises a silicon simple substance and/or a carbon simple substance which are positioned in the pore channels of the inorganic porous material.
Further, the product construction includes at least one of nanoparticles, nanowires, nanotubes, nanofibers, nanoplatelets, films, porous structures, and hollow structures.
The second aspect of the invention provides a preparation method of the alloyed negative electrode material, comprising the following steps:
A. the alloying composite material is obtained by vapor deposition of germanium source gas on a template of an inorganic porous material;
B. and introducing hydrocarbon gas into a container where the alloying composite material is positioned to carry out pyrolytic carbon cladding so as to obtain the alloying negative electrode material.
Further, the temperature of the vapor deposition is 300-500 ℃ and the time is 1-4 h.
The pyrolysis temperature is 550-950 ℃ and the pyrolysis time is 1-3 h.
The flow rate of the germanium source gas is 40sccm-80sccm.
The flow rate of the hydrocarbon gas is 80sccm-200sccm.
Further, the germanium source gas includes at least one of germane, digermane, dimethylgermane, and tetraethylgermane.
The hydrocarbon gas includes at least one of methane, ethane, ethylene, acetylene, propane, and propylene.
Further, in the step a, the method further comprises depositing a silicon source gas and/or a carbon source gas simultaneously when depositing a germanium source gas in a vapor phase.
The silicon source gas includes at least one of silane, disilane, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, methyldisilane, dimethyldisilane, trimethyldisilane, tetramethyldisilane, hexamethylsilane, and ethylsilane.
The carbon source gas includes at least one of methane, ethane, ethylene, acetylene, propane, and propylene.
Further, the flow rate of the silicon source gas is 40sccm-80sccm.
The flow rate of the carbon source gas is 40sccm-600sccm.
The third aspect of the invention provides application of the alloyed negative electrode material in a negative electrode material of a lithium battery.
Compared with the prior art, the invention has at least the following beneficial effects:
the alloying anode material provided by the invention has high theoretical capacity (1600 mAh/g) and high diffusion coefficient (100 cm) 2 S) and high conductivity (2.17. 2.17 s/m) germanium is used in the anode material, an inorganic porous material is used to provide space for the contraction and expansion of germanium, and a carbon coating layer improves the stability of the core layer material. The alloyed negative electrode material has high theoretical capacity and high conductivity, has small volume expansion in the charge and discharge process, and the inorganic porous material weakens the influence of volume change on the material performance, and cooperatively improves the first effect and the reversible capacity of the negative electrode material, thereby greatly improving the cycle stability of the negative electrode material.
The preparation method of the alloying anode material provided by the invention has the advantages of continuous and simple process and high degree of mechanization, saves labor cost, and is suitable for large-scale industrial production.
The alloyed negative electrode material provided by the invention provides a negative electrode material with better performance for the battery, expands the use place and the use condition of the battery, and promotes the development of downstream industry.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a SEM photograph (a), a Ge element distribution photograph (b), a Si element distribution photograph (C) and a C element distribution photograph (d) of the carbon-coated alloyed negative electrode material prepared by using the alumina porous ceramic powder as a template provided in example 7.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments of the present invention.
The terms "comprises," "comprising," "including," or any other variation thereof, are intended to cover a specific feature, number, step, operation, element, component, or combination of the foregoing, which may be used in various embodiments of the present invention, and are not intended to first exclude the presence of or increase the likelihood of one or more other features, numbers, steps, operations, elements, components, or combinations of the foregoing.
Furthermore, the terms "first," "second," "third," and the like are used merely to distinguish between descriptions and should not be construed as indicating or implying relative importance.
The first aspect of the present invention provides an alloyed negative electrode material comprising an alloyed composite material as a core layer; and a carbon cladding layer surrounding the core layer;
the alloying composite material comprises an inorganic porous material and a germanium simple substance positioned in pore channels of the inorganic porous material;
wherein the inorganic porous material comprises one of porous ceramics, porous carbon materials, porous silica materials and molecular sieves;
the elemental germanium accounts for 1wt.% to 90wt.% of the alloyed negative electrode material.
The alloying anode material provided by the invention has high theoretical capacity (1600 mAh/g) and high diffusion coefficient (100 cm) 2 S) and high conductivity (2.17. 2.17 s/m) germanium is used in the anode material, an inorganic porous material is used to provide space for the contraction and expansion of germanium, and a carbon coating layer improves the stability of the core layer material. The alloyed negative electrode material has high theoretical capacity and high conductivity, has small volume expansion in the charge and discharge process, and the inorganic porous material weakens the influence of volume change on the material performance, and cooperatively improves the first effect and the reversible capacity of the negative electrode material, thereby greatly improving the cycle stability of the negative electrode material. When the alloy anode material is used as the anode of a lithium ion battery, the alloy anode material can perform an alloying reaction with lithium ions to store lithium, and has ultrahigh theoretical specific capacity.
When the proportion of the germanium simple substance in the alloying anode material is less than 1 wt%, the germanium simple substance cannot be effectively communicated and contacted, so that the electronic conductivity of the composite alloying anode material cannot be effectively improved, the multiplying power performance of the material is reduced, and in addition, when the proportion of the germanium simple substance is too low, the specific capacity of the composite material cannot be effectively improved, and the energy density of a battery is reduced; when the proportion of the germanium simple substance in the alloying anode material is more than 90 wt%, the inorganic porous material for supporting cannot form stable structures and pore channels in fixed distribution, and further cannot buffer the volume expansion and contraction generated in the charging and discharging processes of the alloy material, so that the rapid collapse of the composite material and the rapid decay of the electrochemical performance are caused.
Typically, but not by way of limitation, the elemental germanium is present in the alloyed negative electrode material in a ratio of 1wt.%, 2wt.%, 5wt.%, 10wt.%, 20 wt.%, 40wt.%, 60wt.%, 80wt.%, or 90wt.%.
Further, the thickness of the carbon coating layer is 1nm-20nm. When the thickness of the carbon coating layer is less than 1nm, a stable and complete carbon coating layer cannot be effectively formed on the surface of a deposited alloying material, so that the material is unstable to air, a severe oxidation reaction can occur after the material contacts with the air, the material is invalid, and meanwhile, the stability of the material to water can be reduced, and the conditions of gas production, pole piece peeling and the like occur when the electrode slurry is prepared; when the thickness of the carbon coating layer is larger than 20nm, the carbon layer can prevent the rapid transmission of lithium ions, so that the rate capability of the composite material is reduced, rapid charge and discharge cannot be realized, and in addition, the specific capacity of the material is reduced and the energy density of the battery is reduced due to the excessively high carbon material ratio. Typically, but not by way of limitation, the carbon coating has a thickness of 1nm, 3nm, 5nm, 7nm, 9nm, 11nm, 13nm, 15nm, 17nm, 19nm or 20nm.
The porous ceramic material includes at least one of porous alumina, porous zirconia, porous magnesia, and porous beryllium oxide.
Further, the porous material also comprises a silicon simple substance and/or a carbon simple substance which are positioned in the pore channels of the inorganic porous material.
Further, the product construction includes at least one of nanoparticles, nanowires, nanotubes, nanofibers, nanoplatelets, films, porous structures, and hollow structures.
The second aspect of the invention provides a preparation method of the alloyed negative electrode material, comprising the following steps:
A. the alloying composite material is obtained by vapor deposition of germanium source gas on a template of an inorganic porous material;
B. and introducing hydrocarbon gas into a container where the alloying composite material is positioned to carry out pyrolytic carbon cladding so as to obtain the alloying negative electrode material.
The preparation method of the alloying anode material provided by the invention has the advantages of continuous and simple process and high degree of mechanization, saves labor cost, and is suitable for large-scale industrial production.
The invention can realize the particle size control and morphology control of the alloying materials by using the chemical vapor deposition technology, and can regulate the size of the formed nano particles by regulating the deposition conditions so as to grow the alloying materials with different morphologies. The gaseous material can be introduced into the interior or surface of the inorganic porous material to crack the material in and on the pore canal of the template, so as to form the alloyed negative electrode material with porous structure and special morphology.
Further, the temperature of the vapor deposition is 300-500 ℃ and the time is 1-4 h. The chemical vapor deposition is formed by cracking a gas source of the germanium material under a high-temperature condition, wherein the high-temperature condition is that the gas source cracking temperature of the germanium material is higher, and the vapor deposition equipment can be a rotary furnace, a fluidized bed type deposition furnace and a horizontal bed type vibration furnace. When the gas sources for vapor deposition are multiple, the temperature of the vapor deposition is higher than the cracking temperature of all the gas sources, so that the vapor deposition of various materials is ensured.
Typically, but not by way of limitation, the vapor deposition temperature is 300 ℃, 350 ℃, 400 ℃, 450 ℃, or 500 ℃; the time is 1h, 2h, 3h or 4h.
The pyrolysis temperature is 550-950 ℃ and the pyrolysis time is 1-3 h. Typically, but not by way of limitation, the hydrocarbon gas pyrolysis temperature is 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ or 950 ℃; the time is 1h, 2h or 3h.
The flow rate of the germanium source gas is 40sccm-1000sccm. When the flow of the germanium source gas is less than 40sccm, the deposition rate of germanium is too low, the germanium is deposited in the form of single particles, an effective continuous deposition layer cannot be formed, the risk of oxidization is increased, and the difficulty of batch preparation is too high; when the flow rate of the germanium source gas is more than 1000sccm, the germane gas cannot be effectively cracked, so that the utilization rate of germane is reduced, and the manufacturing cost is increased. Typically, but not by way of limitation, the flow rate of the germanium source gas is 40sccm, 100sccm, 500sccm, 800sccm, or 1000sccm.
The flow rate of the hydrocarbon gas is 80sccm-200sccm. When the flow rate of the hydrocarbon gas is less than 80sccm, a continuous coating layer cannot be formed on the surface of the alloyed composite anode material, and carbon coating cannot be effectively performed; when the flow rate of hydrocarbon gas is more than 200sccm, the cracking rate of acetylene is reduced, and incomplete cracking of acetylene can cause more hydrocarbon to appear on the surface of the alloy anode material, so that the resistivity of the material is increased. Typically, but not by way of limitation, the hydrocarbon gas flow is 80sccm, 100sccm, 150sccm, 180sccm, or 200sccm.
Further, the germanium source gas includes at least one of germane, digermane, dimethylgermane, and tetraethylgermane.
The hydrocarbon gas includes at least one of methane, ethane, ethylene, acetylene, propane, and propylene.
Further, in the step a, the method further comprises depositing a silicon source gas and/or a carbon source gas simultaneously when depositing a germanium source gas in a vapor phase.
The silicon source gas includes at least one of silane, disilane, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, methyldisilane, dimethyldisilane, trimethyldisilane, tetramethyldisilane, hexamethylsilane, and ethylsilane.
The carbon source gas includes at least one of methane, ethane, ethylene, acetylene, propane, and propylene.
Further, the flow rate of the silicon source gas is 40sccm-1000sccm. When the flow of the silicon source gas is less than 40sccm, the deposition rate of silicon is too low, silicon is deposited in the form of single particles, an effective continuous deposition layer cannot be formed, the risk of oxidization is increased, and the difficulty of batch preparation is too high; when the flow rate of the silicon source gas is more than 1000sccm, the silane gas cannot be effectively cracked, so that the utilization rate of the silane is reduced, and the manufacturing cost is increased. Typically, but not by way of limitation, the flow rate of the silicon source gas is 40sccm, 100sccm, 200sccm, 500sccm, or 1000sccm.
During the deposition process, the gas flow rate is related to the mass ratio of germanium to silicon carbon in the finally formed alloyed negative electrode material. In the implementation process of the invention, the alloyed negative electrode materials with different germanium-silicon-carbon contents are obtained by adjusting the flow and time of the germanium source gas, the silicon source gas and the carbon source gas.
The flow rate of the carbon source gas is 40sccm-600sccm.
The third aspect of the invention provides application of the alloyed negative electrode material in a negative electrode material of a lithium battery.
The alloyed negative electrode material provided by the invention provides a negative electrode material with better performance for the battery, expands the use place and the use condition of the battery, and promotes the development of downstream industry.
The invention is further illustrated by the following specific examples and comparative examples, however, it should be understood that these examples are for the purpose of illustration only in greater detail and should not be construed as limiting the invention in any way. The raw materials used in the examples and comparative examples of the present invention were conducted under conventional conditions or conditions recommended by the manufacturer, without specifying the specific conditions. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides an alloying anode material, and the preparation method comprises the following steps:
1. 100g of alumina porous ceramic powder (Jiangxi Bao HongXue nano technology Co., ltd./LA 50) is added into a fluidized bed type chemical vapor deposition device, the temperature is raised to 370 ℃, germane gas and ethylene gas are simultaneously introduced into the fluidized bed type chemical vapor deposition device under the protection of nitrogen, wherein the flow rate of the germane gas is controlled to be 500sccm, the flow rate of the ethylene gas is controlled to be 100sccm, and the introduction of the germane gas and the ethylene gas is stopped after 1h is jointly deposited.
2. Taking out the deposited material, crushing the material to Dv50= um by using a jet mill, then adding the material into a rotary coating furnace, heating the material to 850 ℃ under the protection of nitrogen, introducing acetylene gas at the gas flow of 100sccm for gas phase coating, introducing 2h, and stopping introducing acetylene to obtain carbon-coated alloyed negative electrode material powder particles prepared by taking alumina porous ceramic powder as a template.
Example 2
This example provides an alloyed negative electrode material, which is different from example 1 in that 100g of porous silica powder (Jiangsu-mai powder technology Co., ltd.) was used instead of 100g of alumina porous ceramic powder, and finally carbon-coated alloyed negative electrode material powder particles made of porous silica powder as a template were obtained. The other raw materials and steps are the same as those of example 1, and are not described in detail herein.
Example 3
This example provides an alloyed negative electrode material, which is different from example 1 in that 100g of porous carbon microspheres (Guangdong Han Yan active carbon technologies Co., ltd./HY-001) are used instead of 100g of alumina porous ceramic powder, and finally carbon-coated alloyed negative electrode material powder particles made of porous carbon microspheres as templates are obtained. The other raw materials and steps are the same as those of example 1, and are not described in detail herein.
Example 4
The embodiment provides an alloying anode material, and the preparation method comprises the following steps:
1. 100g of alumina porous ceramic powder is added into fluidized bed chemical vapor deposition equipment, the temperature is raised to 370 ℃, tetraethyl germane gas and ethylene gas are simultaneously introduced into the fluidized bed chemical vapor deposition equipment under the protection of nitrogen, wherein the flow rate of the tetraethyl germane gas is controlled to be 300 sccm, and the introduction of the tetraethyl germane gas is stopped after 3h is deposited.
2. As in example 1.
Example 5
The embodiment provides an alloying anode material, and the preparation method comprises the following steps:
1. heating the fluidized bed chemical vapor deposition equipment to 370 ℃, and simultaneously introducing germane gas and ethylene gas into the fluidized bed chemical vapor deposition equipment under the protection of nitrogen, wherein the flow rate of the germane gas is controlled to be 500sccm, the flow rate of the ethylene gas is controlled to be 500sccm, and after 3h is jointly deposited, the introduction of the germane gas and the ethylene gas is stopped.
2. And (3) heating to 850 ℃ under the protection of nitrogen, introducing acetylene gas at the gas flow of 100sccm for gas phase cladding, and stopping introducing acetylene after introducing 2h to obtain the carbon-clad and spontaneously grown nanoscale fibrous alloying anode material.
Example 6
The embodiment provides an alloying anode material, and the preparation method comprises the following steps:
1. 100g of alumina porous ceramic powder is added into a fluidized bed chemical vapor deposition device, the temperature is raised to 370 ℃, germane gas is introduced into the fluidized bed chemical vapor deposition device under the protection of nitrogen, wherein the flow of the germane gas is controlled to be 500sccm, and the introduction of the germane gas is stopped after 1h is deposited.
2. Taking out the deposited material, crushing the material to Dv50= um by using a jet mill, then adding the material into a rotary coating furnace, heating the material to 850 ℃ under the protection of nitrogen, introducing acetylene gas at the gas flow of 100sccm for gas phase coating, introducing 2h, and stopping introducing acetylene to obtain carbon-coated alloyed negative electrode material powder particles prepared by taking alumina porous ceramic powder as a template.
Example 7
The embodiment provides an alloying anode material, and the preparation method comprises the following steps:
1. 100g of alumina porous ceramic powder is added into a fluidized bed chemical vapor deposition device, the temperature is raised to 370 ℃, tetraethyl germane gas and tetramethylsilane gas are simultaneously introduced into the fluidized bed chemical vapor deposition device under the protection of nitrogen, wherein the flow rate of the tetraethyl germane gas is controlled to be 500sccm, the flow rate of the tetramethylsilane gas is controlled to be 400 sccm, and the introduction of the tetraethyl germane gas and the tetramethylsilane gas is stopped after 1h is jointly deposited.
2. As in example 1.
SEM and elemental distribution measurements were made on carbon-coated, alloyed negative electrode material powder particles prepared from alumina porous ceramic powder obtained in example 7, and the resulting photographs were shown in FIG. 1. As can be seen from fig. 1 (b), fig. 1 (c) and fig. 1 (d), germanium, silicon and carbon elements are uniformly deposited on the template, and the elements are uniformly distributed, so that no obvious agglomeration occurs.
Comparative example 1
The comparative example provides a silicon-carbon negative electrode material, which is prepared by the following steps:
1. 100g of alumina porous ceramic powder is added into a fluidized bed chemical vapor deposition device, the temperature is raised to 370 ℃, and silane gas and ethylene gas are simultaneously introduced into the fluidized bed chemical vapor deposition device under the protection of nitrogen, wherein the flow rate of the silane gas is controlled to be 500sccm, the flow rate of the ethylene gas is controlled to be 40sccm, and the introduction of the silane gas and the ethylene gas is stopped after the co-deposition of 3h.
2. Taking out the deposited material, crushing the material to Dv50= um by using a jet mill, then adding the material into a rotary coating furnace, heating the material to 850 ℃ under the protection of nitrogen, introducing acetylene gas at the gas flow of 100sccm for gas phase coating, introducing 2h, and stopping introducing acetylene to obtain carbon-coated silicon-carbon negative electrode material powder particles prepared by taking alumina porous ceramic powder as a template.
Comparative example 2
The comparative example provides a silicon-carbon negative electrode material, which is prepared by the following steps:
1. under the protection of nitrogen, introducing silane gas and ethylene gas into the fluidized bed chemical vapor deposition equipment at the same time, wherein the flow rate of the silane gas is controlled to be 500sccm, the flow rate of the ethylene gas is controlled to be 40sccm, and after 3h of co-deposition, the introduction of the silane gas and the ethylene gas is stopped.
2. Taking out the deposited material, crushing the material to Dv50= um by using a jet mill, then adding the material into a rotary coating furnace, heating the material to 850 ℃ under the protection of nitrogen, introducing acetylene gas at the gas flow of 100sccm for gas phase coating, and stopping introducing acetylene after introducing 2h to obtain carbon-coated silicon-carbon negative electrode material powder particles prepared without a template.
Comparative example 3
The comparative example provides an alloyed negative electrode material, which is prepared by the following steps:
1. under the protection of nitrogen, germane gas and ethylene gas are simultaneously introduced into the fluidized bed chemical vapor deposition equipment, wherein the flow rate of the germane gas is controlled to be 500sccm, the flow rate of the ethylene gas is controlled to be 100sccm, and the germane gas and the ethylene gas are stopped from being introduced after being co-deposited by 1 h.
2. Taking out the deposited material, crushing the material to Dv50= um by using a jet mill, then adding the material into a rotary coating furnace, heating the material to 850 ℃ under the protection of nitrogen, introducing acetylene gas at the gas flow of 100sccm for gas phase coating, and stopping introducing acetylene after introducing 2h to obtain the carbon-coated and template-free alloyed negative electrode material powder particles.
Test example 2
The negative electrode materials provided in examples 1 to 7 and comparative examples 1 to 3 were assembled into a battery, and the procedure was as follows:
1. preparing a pole piece: the negative electrode material, the conductive agent (Super-P) and the polyacrylic acid (PAA) binder are mixed according to the mass ratio of 80:10:10, uniformly stirring and coating the mixture on a copper foil current collector, airing at room temperature, placing the copper foil current collector into a vacuum oven, and further drying at 60 ℃ for 12 hours to obtain the pole piece.
2. And (3) battery assembly: cutting the obtained pole piece into round pole piece with diameter of 10 mm, and active material loading of 1.3 mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Metallic lithium sheet as counter electrode, 1 mol/L LiPF 6 (the solvent was a mixed solution of ethylene carbonate and diethyl carbonate in a volume ratio of 1:1, 5% by volume of fluoroethylene carbonate was added as an electrolyte, a polypropylene microporous separator was assembled into 2032-type coin cells in a glove box under an argon atmosphere, and 50 μl of the electrolyte was added to each cell.
And (3) carrying out electrical property test on the obtained 2032 type button battery: the charge and discharge cut-off voltages were 1.5V and 0.005V, respectively, and then activation was performed at 0.05C magnification and charge and discharge cycle test was performed at 0.5C magnification.
The results are shown in Table 1 below.
Table 1 table of electrical properties
As can be seen from table 1, the deposition of germanium is not greatly affected by different templates, and the capacity efficiency and the capacity retention after 100 cycles are all at approximate levels; the capacity and efficiency of the material obtained by simultaneously cracking tetraethyl germane and ethylene are lower, but the capacity retention rate is higher; increasing the amount of germanium deposited can effectively increase the capacity of the material, but excessive germanium deposition can reduce the first coulombic efficiency and capacity retention of the material; simultaneously performing germanium/carbon deposition has reduced capacity and first coulombic efficiency, but higher capacity retention compared to performing germanium deposition alone; meanwhile, the germanium/silicon/carbon multi-element deposition is carried out, and as the specific capacity of silicon is higher, higher capacity and first coulombic efficiency can be realized on smaller deposition amount, and the capacity retention rate is higher; in addition, the capacity retention of silicon co-deposited with carbon is lower than that of germanium co-deposited with carbon; silicon and carbon may form silicon carbide when deposited without the template resulting in reduced capacity, efficiency and capacity retention, while germanium and carbon may exhibit normal capacity and have higher capacity retention due to low cracking temperatures.
Finally, it should be noted that: the above examples are only specific embodiments of the present invention, and are not intended to limit the scope of the present invention, but it should be understood by those skilled in the art that the present invention is not limited thereto, and that the present invention is described in detail with reference to the foregoing examples: any person skilled in the art may modify or easily conceive of the technical solution described in the foregoing embodiments, or perform equivalent substitution of some of the technical features, while remaining within the technical scope of the present disclosure; such modifications, changes or substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention, and are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. An alloyed negative electrode material characterized by comprising an alloyed composite material as a core layer; and a carbon cladding layer surrounding the core layer;
the alloying composite material comprises an inorganic porous material and a germanium simple substance positioned in pore channels of the inorganic porous material;
wherein the inorganic porous material comprises one of porous ceramics, porous carbon materials, porous silica materials and molecular sieves;
the elemental germanium accounts for 1wt.% to 90wt.% of the alloyed negative electrode material.
2. The alloyed negative electrode material of claim 1 wherein the thickness of the carbon coating layer is 1nm-20nm;
the porous ceramic includes at least one of porous alumina, porous zirconia, porous magnesia, and porous beryllium oxide.
3. The alloyed negative electrode material of claim 1 further comprising elemental silicon and/or elemental carbon within the pores of the inorganic porous material.
4. The alloyed negative electrode material of any of claims 1-3 wherein the product configuration comprises at least one of nano-particles, nano-wires, nano-tubes, nano-fibers, nano-sheets, films, porous structures and hollow structures.
5. A method for producing the alloyed negative electrode material according to any one of claims 1 to 4, comprising the steps of:
A. the alloying composite material is obtained by vapor deposition of germanium source gas on a template of an inorganic porous material;
B. and introducing hydrocarbon gas into a container where the alloying composite material is positioned to carry out pyrolytic carbon cladding so as to obtain the alloying negative electrode material.
6. The method according to claim 5, wherein the vapor deposition is carried out at a temperature of 300 ℃ to 500 ℃ for a time of 1h to 4h;
the temperature of the pyrolytic carbon coating is 550-950 ℃ and the time is 1-3 h;
the flow rate of the germanium source gas is 40sccm-1000sccm;
the flow rate of the hydrocarbon gas is 80sccm-200sccm.
7. The method of claim 5, wherein the germanium source gas comprises at least one of germane, digermane, dimethylgermane, and tetraethylgermane;
the hydrocarbon gas includes at least one of methane, ethane, ethylene, acetylene, propane, and propylene.
8. The method of claim 5, further comprising simultaneously depositing a silicon source gas and/or a carbon source gas during vapor deposition of the germanium source gas in step a;
the silicon source gas comprises at least one of silane, disilane, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, methyldisilane, dimethyldisilane, trimethyldisilane, tetramethyldisilane, hexamethylsilane and ethylsilane;
the carbon source gas includes at least one of methane, ethane, ethylene, acetylene, propane, and propylene.
9. The method of claim 8, wherein the flow rate of the silicon source gas is 40sccm to 1000sccm;
the flow rate of the carbon source gas is 40sccm-600sccm.
10. Use of the alloyed negative electrode material of any one of claims 1-4 or the alloyed negative electrode material prepared by the preparation method of any one of claims 5-9 in a negative electrode material of a lithium battery.
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