CN112886012A - Silicon-based lithium ion battery cathode material with high first coulombic efficiency and preparation method thereof - Google Patents

Silicon-based lithium ion battery cathode material with high first coulombic efficiency and preparation method thereof Download PDF

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CN112886012A
CN112886012A CN202110055612.0A CN202110055612A CN112886012A CN 112886012 A CN112886012 A CN 112886012A CN 202110055612 A CN202110055612 A CN 202110055612A CN 112886012 A CN112886012 A CN 112886012A
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silicon
transition metal
metal
coulombic efficiency
lithium ion
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赵海雷
杨朝
李兆麟
谢洪亮
杜志鸿
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University of Science and Technology Beijing USTB
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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    • 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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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a silicon-based lithium ion battery cathode material with high initial coulombic efficiency and a preparation method thereof, belonging to the technical field of battery material preparation. According to the invention, the silicon-based negative electrode material coated with the transition metal or the compound thereof is obtained by adopting a chemical vapor deposition method, wherein the transition metal is in a simple substance state under a silicon lithium-intercalation potential, the conductivity of the material is improved, the local stress is relieved, and cracks generated in the lithium-intercalation and lithium-deintercalation process are reduced; and can participate in reversible lithium intercalation and deintercalation reaction, activate inert products generated by the material in the lithium intercalation process, and improve the first coulombic efficiency of the silicon-based material. The transition metal or the compound thereof has good bonding with the silicon substrate, and meanwhile, the process steps are simple, the controllability is strong, the product composition can be regulated and controlled only by regulating the gas components participating in the reaction, and the method is suitable for large-scale industrialization.

Description

Silicon-based lithium ion battery cathode material with high first coulombic efficiency and preparation method thereof
Technical Field
The invention belongs to the technical field of battery material preparation, and particularly relates to a silicon-based lithium ion battery cathode material with high first coulombic efficiency and a preparation method thereof.
Background
Among secondary batteries, lithium ion batteries have the advantages of high energy density, high power density, long cycle life, convenient maintenance and the like, and are widely applied to intelligent electronic devices such as mobile phones, notebook computers, digital cameras and the like. With the development of high-power mobile electric equipment, especially electric automobiles, people have made higher requirements on the rate capability, energy density, power density and other properties of lithium ion batteries. However, the performance of graphite negative electrodes in commercial lithium ion batteries is difficult to meet these requirements, and development of a new generation of high-performance lithium ion battery negative electrode material becomes a research hotspot.
In the lithium ion battery cathode material, silicon has the advantages of ultrahigh specific capacity (the theoretical value is 4200mAh/g), proper lithium intercalation potential, abundant resources, environmental friendliness and the like, and is concerned by scholars at home and abroad. However, silicon has a problem of large volume change during the lithium extraction/insertion process, which not only causes silicon particles to be broken and pulverized and to be peeled off from a current collector, but also causes the continuous fracture and proliferation of a surface Solid Electrolyte Interface (SEI) film, so that the silicon-based material has low coulombic efficiency and finally causes the degradation of cycle performance. Nano-crystallization of silicon material, design of porous structure, addition of conductive phase and preparation of silicon oxide (SiO)x，0<x<2) The method can properly relieve or solve the problem of poor cycle performance of the silicon-based material, but improves the first library of the silicon-based materialThe effect is very slight in terms of efficiency. The lower first coulombic efficiency of the silicon-based negative electrode material leads to more irreversible lithium, and more positive electrode materials are needed for the battery to reach the expected energy density, so that the overall energy density of the battery is reduced, and the preparation cost of the battery is further increased.
The silicon protoxide material has the most practical prospect in the silicon-based material, and can generate an inert component in situ in the lithium removal/insertion process, thereby properly relieving or solving the problem of poor cycle performance of the silicon-based material. But SiOxFormation of Li during the first intercalation of lithium2The irreversible reaction of O and lithium silicate consumes active lithium ions to form 'dead lithium', so that the initial coulomb efficiency of the battery is greatly reduced, and is generally only 50-80%. By chemical lithium supplementation (ACS Applied Materials)&Interfaces 11(2019) 18305-18312; angewandte Chemie International Edition 59(2020) 14473-; the initial coulombic efficiency of The material can be improved by carrying out The prelithiation of The electrode of The silicon-based material in The mode of Journal of The Electrochemical Society 154(2007) A376-A380).
In addition, the irreversible reaction is reduced by changing the composition of the silicon-based material, and the method is also an important method for improving the first coulombic efficiency. Wherein, the transition metal, the lithium oxide and the lithium silicate have the function of reversible conversion, and the purpose of improving the initial coulomb efficiency of the material can be realized by introducing the transition metal into the silicon-based material. There are many technological methods for introducing metal elements into silicon-based materials, and most of them are prepared by mechanical ball milling (such as chinese patent applications CN106941157A, CN103650217A, CN108807952A and CN103682279A) or liquid phase evaporation and calcination (such as chinese patent applications CN110391406A and CN 110021737A). Among them, the high-energy ball milling equipment relied on by the mechanical ball milling method is expensive and does not utilize mass production. Most of materials prepared by the liquid phase evaporation-drying and calcination method are limited to metal oxides, and the steps of reduction, vulcanization, nitridation and the like are further added to obtain metal simple substances, metal sulfides, metal nitrides and the like, so that the preparation process is complex.
Taking the Chinese patent application CN109686959A as an example, the invention discloses a metal modificationThe silicon oxide negative electrode material is prepared by a method of carrying out high-energy ball milling on silicon monoxide particles and metal powder under the protection of inert atmosphere. Wherein the metal particles are in brittle SiOxIs cut into extremely fine nano particles under the impact of the high-energy balls and is uniformly compounded on SiOxIn the bulk phase. By means of nano-metal particles with Li2The reversible conversion process of O releases Li, thereby greatly improving SiOxFirst coulombic efficiency of the negative electrode material. Meanwhile, the conductivity of the battery is improved, the ion diffusion is accelerated, and the problem of volume expansion of the silicon-based material is better relieved, so that the cycle performance of the battery is improved. The high-energy ball milling equipment has high price, and the used metal nano powder has high chemical activity and is not suitable for large-scale production.
Therefore, how to effectively compound the silicon-based material and the metal or the metal compound so as to improve the initial coulomb efficiency of the cathode material, develop a preparation process which has simple process flow and can realize continuous production, is always a difficult point for researching the cathode material of the silicon-based lithium ion battery, and has important significance.
Disclosure of Invention
Aiming at the problems that high-energy ball milling equipment is dependent on or the process flow is complex and large-scale production cannot be realized in the composite process of a silicon-based material and a metal element in the prior art, the invention provides a silicon-based lithium ion battery cathode material with high initial coulombic efficiency and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
one aspect of the invention provides a silicon-based lithium ion battery cathode material with high initial coulombic efficiency, which comprises a silicon matrix material and transition metal or compound particles thereof coated on the silicon matrix material; wherein the transition metal or the compound particles thereof are deposited on the surface of the silicon substrate material by means of CVD.
Further, the mass percentages of the elements in the negative electrode material are as follows: si: 10-99.99%; 0.01-30% of transition metal; o: 0 to 50 percent; c: 0 to 70 percent; n: 0 to 15 percent; s: 0 to 15 percent; p: 0 to 15 percent.
Further, the transition metal elements comprise one or more of Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Cu, Ag, Au and Pt.
Further, the transition metal is a metal simple substance, and the transition metal compound includes one or more of a metal-carbon alloy, a metal-silicon alloy, a metal nitride, a metal oxide, a metal phosphide, a metal sulfide, and a metal silicate.
Preferably, the transition metal compound is present as a non-metal oxide.
The invention also provides a preparation method of the silicon-based lithium ion battery cathode material with high first coulombic efficiency, which comprises the following steps: the transition metal source is subjected to CVD deposition reaction on the silicon substrate material to obtain a silicon-based negative electrode material coated with transition metal or compound; the temperature of the deposition reaction is 120-1300 ℃, the time of the deposition reaction is not less than 0.1h, the temperature rising/reducing rate in the reaction process is controlled to be 1-100 ℃/min, and the air pressure in the deposition furnace is not higher than 200 kPa.
Further, the transition metal source is a transition metal compound having a vaporization/sublimation temperature in the range of 50 to 600 ℃, and includes one or more of an organometallic compound, an inorganic metal complex, and an inorganic metal compound.
Furthermore, if the transition metal source is a solid metal compound which is easy to gasify and sublimate, such as cobalt carbonyl, ferrocene, nickel acetylacetonate, etc., it is not necessary to use an additional device, and the metal source is directly placed in a proper temperature area (gasification position) in the gas inlet direction of the deposition furnace to gasify the metal source (the schematic diagram of the CVD reaction device shown in fig. 3); if the transition metal source is a normal temperature liquid metal compound, such as carbonyl iron, dimethyl zinc, TiCl4、VCl3Then a gasification furnace is needed to be arranged in front of the gas inlet of the deposition furnace to obtain the gaseous metal source (shown as C in figure 2)Schematic view of a VD reaction apparatus). Elemental sulfur, elemental phosphorus, silane or chlorosilane which are easy to gasify can be additionally placed in the gasification position or the gasification furnace so as to obtain metal sulfide, metal phosphide or metal-silicon alloy and the like.
Furthermore, the silicon substrate material is less limited when the CVD reaction is used for preparing the composite material. The silicon substrate material is simple substance silicon, carbon composite material thereof and silicon oxide (SiO)x，0<x is less than or equal to 2) and carbon composite material with the grain diameter of 0.05-20 mu m. Preferably, the silicon substrate material is a nano material and a porous material with large specific surface area, and comprises simple substance silicon powder with the particle size of 50-500nm prepared by a steam method, simple substance silicon or sub-silicon oxide powder which is mechanically crushed to the particle size of 100-10000nm, and porous silicon or sub-silicon oxide with the pore size of 10-1000nm obtained by a magnesiothermic reduction method.
Furthermore, the ratio of the initial transition metal source to the silicon substrate material varies greatly due to the different deposition rates of the deposition metals from the different metal sources. The mass ratio of the transition metal source to the added amount of the bulk material is 0.005-1000.
Further, the initial environment of the deposition reaction may be vacuum, and the low pressure CVD reaction is completed when the vaporization temperature of the metal source reaches the vaporization temperature.
Further, the filling gas and the purging carrier gas in the deposition reaction are selected from one or more of hydrogen, nitrogen, argon, helium, neon, oxygen, krypton, xenon, ammonia, hydrogen sulfide and phosphine, and the gas flow rate is controlled within the range of 1-1000 sccm.
Compared with the prior art, the technical scheme of the application has the following beneficial effects or technical advantages:
the lithium ion battery cathode material is a silicon-based material coated by transition metal or a compound thereof, wherein the transition metal is in a simple substance state under a silicon lithium-intercalation potential, so that the conductivity of the material is improved, local stress is relieved, and cracks generated in the lithium-intercalation and lithium-deintercalation process are reduced; and can participate in reversible lithium intercalation and deintercalation reaction, activate inert products (lithium oxide and lithium silicate) generated by the material in the lithium intercalation process, and improve the first coulomb efficiency of the silicon-based material.
The method synthesizes the silicon-based material modified by the transition metal or the compound thereof by a vapor deposition method, has simple steps and strong controllability, can regulate and control the product composition only by regulating the gas components participating in the reaction, is suitable for large-scale industrialization, and can realize continuous production by combining the technologies such as a fluidized bed and the like. The waste generated in the process only has partial waste gas, basically does not generate waste water and solid waste, and easily meets the requirement of green production.
The silicon-based negative electrode material of the lithium ion battery prepared by the invention has a series of advantages of high first coulombic efficiency, good rate capability, high lithium storage capacity and the like.
Drawings
FIG. 1 is a schematic structural diagram of a silicon-based lithium ion battery cathode material according to the present invention;
FIG. 2 is a schematic diagram of a CVD reaction device comprising a gasification furnace used in the preparation process of the silicon-based lithium ion battery cathode material;
FIG. 3 is a schematic diagram of a low-pressure CVD reaction device used in the preparation process of the silicon-based lithium ion battery cathode material according to the invention;
FIG. 4 is a graph showing charge and discharge curves before and after modification of a silicon substrate material;
FIG. 5 is a SEM image of a silicon substrate according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below.
The invention provides a silicon-based lithium ion battery cathode material with high initial coulombic efficiency and a preparation method thereof, wherein the cathode material comprises a silicon matrix material and transition metal or compound particles thereof (the structure schematic diagram is shown in figure 1) coated on the silicon matrix material; wherein the transition metal or the compound particles thereof are deposited on the surface of the silicon substrate material by means of CVD. The negative electrode material has a series of advantages of high coulombic efficiency for the first time, good rate capability, high lithium storage capacity and the like. And the preparation process has simple steps and strong controllability, can regulate and control the composition of the product only by regulating the gas components participating in the reaction, and is suitable for large-scale industrialization.
[ example 1 ]
Mixing nano silicon dioxide (n-SiO)2) Treating at 600 deg.C for 2h to remove impurities such as water and organic substances adsorbed on the surface, weighing 0.1g, uniformly spreading in an alumina crucible, and placing at the deposition position of CVD furnace. Ferrocene (Fe (C)5H5)2) As a metal source, 1g was taken and placed in a gasifier to obtain a reaction gas at 180 ℃ which is slightly higher than the sublimation temperature of ferrocene. The overall CVD apparatus is described with reference to FIG. 2.
Taking hydrogen-argon mixed gas containing 5% hydrogen as carrier gas, introducing into CVD furnace at a gas flow of 50sccm, heating to 500 deg.C at a heating rate of 5 deg.C/min, maintaining for 2h, cooling to room temperature at 5 deg.C/min, and taking out black SiO samplexFe。
Weighing active Substance (SiO) at a mass ratio of 70:15:152Fe), acetylene black and CMC, mixing them with proper amount of water uniformly to obtain slurry, coating it on copper foil uniformly, vacuum drying, punching to obtain circular electrode plate, using metal lithium as counter electrode and 1mol/L LiPF6And EMC + DMC + EC (volume ratio of 1:1:1) is used as electrolyte, and Celgard 2400 is used as a diaphragm to form the button half cell.
Comparative example 1
Mixing nano silicon dioxide (n-SiO)2) Treating at 600 deg.C for 2h to remove impurities such as water and organic substances adsorbed on the surface, weighing 0.1g, uniformly spreading in an alumina crucible, and placing at the deposition position of CVD furnace.
Taking hydrogen-argon mixed gas containing 5% hydrogen as carrier gas, introducing into a CVD furnace at a gas flow of 50sccm, heating to 500 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 2h, cooling to room temperature at a cooling rate of 5 ℃/min, and taking out a white sample SiOx。
The above SiO was prepared in exactly the same manner as in example 12The sample is an electrode of an active material and a corresponding battery.
Constant current charging and discharging tests are respectively carried out on the assembled batteries in the embodiment 1 and the comparative example 1, and the charging and discharging voltage range is 0.01-3V. The results show that SiO, as shown in FIG. 42The first discharge specific capacity is only 3 under the current density of 0.1A/g40mAh/g, the first coulombic efficiency is 48.1 percent, and the specific capacity is less than 200mAh/g after 100 times of circulation. SiO 22The Fe electrode material has good electrochemical performance, the first specific discharge capacity is 983.6mAh/g under the current density of 0.1A/g, the first coulombic efficiency is 67.8%, and the specific capacity is 700mAh/g after 100 times of circulation. The sample introduced with the transition metal iron not only improves the initial coulomb efficiency by about 20 percent, but also improves the cycle stability.
[ example 2 ]
Taking SiO (SiO, Alfa, 325 mesh) powder to ball mill, obtaining powder with the particle size less than 2 mu m as a silicon source material, weighing 0.1g and uniformly spreading in an alumina crucible. Titanium tetrachloride (TiCl)4) As a metal source, 7mL of TiCl4The reaction gas is obtained in a gasification furnace at a temperature slightly higher than the gasification temperature of the metal source, and the apparatus is referred to fig. 2.
Placing an alumina crucible in a CVD furnace thermostatic zone, taking a hydrogen-nitrogen mixed gas containing 10% hydrogen as a carrier gas at a gas flow of 100sccm, heating at a rate of 5 ℃/min, introducing gasified titanium tetrachloride into the CVD furnace at a gas flow of 1sccm when the temperature of the CVD furnace is raised to 1100 ℃ until the heat preservation is finished, preserving the heat at the temperature for 2h, cooling to room temperature at a speed of 5 ℃/min, and taking out the SiO-Ti material.
An electrode and a corresponding battery using a SiO-Ti material as an active material were prepared in the same manner as in example 1.
The SiO-Ti battery completes constant current charge and discharge test within the charge and discharge voltage range of 0.01-1.5V. The result shows that the first reversible specific capacity of the SiO-TiN material is 1550mAh/g under the current density of 0.1A/g, the first coulombic efficiency is 69.1 percent, and the specific capacity is 756mAh/g after 50 times of circulation. Titanium tetrachloride (TiCl)4) In the presence of hydrogen (H)2) Is a reducing agent and nitrogen (N)2) The titanium nitride can be obtained by Chemical Vapor Deposition (CVD), and the SiO-Ti material is actually a silicon-based material coated with titanium nitride on the surface, and the SEM image of the material is shown in the attached figure 5.
[ example 3 ]
Taking simple substance nano silicon as a silicon source material, weighing 0.2g of the simple substance nano silicon, and uniformly paving the simple substance nano silicon in an alumina crucible; nickel acetylacetonate (C)15H21CoO6) Is a metal source, and 10 is takeng, placing in a small quartz boat. The alumina crucible and the quartz boat are respectively arranged in a constant temperature zone of the deposition furnace and two metal source gasification temperature (200-. Heating to 500 ℃ at the heating rate of 5 ℃/min under the low pressure of 1000Pa, preserving heat for 3h at the temperature, then closing a heating device, cooling to room temperature along with the furnace, and taking out the nSi-Co material.
An electrode and a corresponding battery using the nSi — Co material as an active material were prepared in the same manner as in example 1.
And carrying out constant-current charge and discharge tests on the assembled battery, wherein the charge and discharge voltage range is 0.01-3V. The result shows that the first discharge specific capacity of the nSi-Co material is 2925mAh/g under the current density of 0.1A/g, the first coulombic efficiency reaches 83.5 percent, and the specific capacity of the material is 2340mAh/g after circulation for 100 times.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. The silicon-based lithium ion battery cathode material with high initial coulombic efficiency is characterized in that the cathode material comprises a silicon matrix material and transition metal or compound particles thereof coated on the silicon matrix material; wherein the transition metal or the compound particles thereof are deposited on the surface of the silicon substrate material by means of CVD.
2. The silicon-based lithium ion battery anode material with high initial coulombic efficiency according to claim 1, wherein the mass percentage of each element in the anode material is as follows: si: 10-99.99%; transition metal: 0.01-30%; o: 0 to 50 percent; c: 0 to 70 percent; n: 0 to 15 percent; s: 0 to 15 percent; p: 0 to 15 percent.
3. The silicon-based lithium ion battery anode material with high first coulombic efficiency of claim 2, wherein the transition metal elements comprise one or more of Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Cu, Ag, Au and Pt.
4. The silicon-based lithium ion battery anode material with high initial coulombic efficiency of claim 3, wherein the transition metal is a metal simple substance, and the transition metal compound comprises one or more of metal-carbon alloy, metal-silicon alloy, metal nitride, metal oxide, metal phosphide, metal sulfide and metal silicate.
5. The silicon-based lithium ion battery anode material with high first coulombic efficiency of claim 4, wherein the transition metal compound particles are in the form of non-metal oxide.
6. A method for preparing the silicon-based lithium ion battery anode material with high initial coulombic efficiency according to any one of claims 1 to 5, wherein the method comprises the following steps: the transition metal source is subjected to CVD deposition reaction on the silicon substrate material to obtain a silicon-based negative electrode material coated with the transition metal or the compound thereof; the temperature of the deposition reaction is 120-1300 ℃, the time of the deposition reaction is not less than 0.1h, the temperature rising/reducing rate in the reaction process is controlled to be 1-100 ℃/min, and the air pressure in the deposition furnace is not higher than 200 kPa.
7. The preparation method of the silicon-based lithium ion battery anode material with high initial coulombic efficiency according to claim 6, wherein the transition metal source is a transition metal compound with a vaporization/sublimation temperature in the range of 50-600 ℃, and comprises one or more of organic metal compounds, inorganic metal complexes and inorganic metal compounds.
8. The preparation method of the silicon-based lithium ion battery anode material with high initial coulombic efficiency according to claim 6, wherein the silicon-based material comprises elemental silicon and carbon composite material thereof or silicon oxide (SiO)x，0<x is less than or equal to 2) and carbon composite materials thereof; the grain diameter of the silicon matrix material is 0.05-20μm。
9. The preparation method of the silicon-based lithium ion battery anode material with high initial coulombic efficiency according to claim 6, wherein the mass ratio of the transition metal source to the added amount of the silicon-based matrix material is 0.005-1000.
10. The method for preparing the silicon-based lithium ion battery cathode material with high initial coulombic efficiency as claimed in claim 6, wherein the filling gas and purge carrier gas in the deposition reaction are selected from one or more of hydrogen, nitrogen, argon, helium, neon, oxygen, krypton, xenon, ammonia, hydrogen sulfide and phosphine, and the gas flow rate is controlled within the range of 1-1000 sccm.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113684471A (en) * 2021-08-02 2021-11-23 江苏鎏溪光学科技有限公司 System and method for monitoring reaction atmosphere in chemical vapor deposition process
CN114497484A (en) * 2022-01-04 2022-05-13 广东东岛新能源股份有限公司 Silica-based composite anode material and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102122708A (en) * 2010-01-08 2011-07-13 中国科学院物理研究所 Negative pole material for lithium-ion secondary battery, negative pole containing negative pole material, preparation method of negative pole and battery containing negative pole
CN107799723A (en) * 2016-08-30 2018-03-13 华为技术有限公司 A kind of silicon substrate composite negative plate and preparation method thereof and lithium rechargeable battery
CN111342020A (en) * 2020-03-11 2020-06-26 中国科学院宁波材料技术与工程研究所 Silicon-based negative electrode material, preparation method thereof and lithium ion battery
CN111540889A (en) * 2020-05-08 2020-08-14 珠海冠宇电池股份有限公司 Silicon negative electrode material coated by double-layer coating layer and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102122708A (en) * 2010-01-08 2011-07-13 中国科学院物理研究所 Negative pole material for lithium-ion secondary battery, negative pole containing negative pole material, preparation method of negative pole and battery containing negative pole
CN107799723A (en) * 2016-08-30 2018-03-13 华为技术有限公司 A kind of silicon substrate composite negative plate and preparation method thereof and lithium rechargeable battery
CN111342020A (en) * 2020-03-11 2020-06-26 中国科学院宁波材料技术与工程研究所 Silicon-based negative electrode material, preparation method thereof and lithium ion battery
CN111540889A (en) * 2020-05-08 2020-08-14 珠海冠宇电池股份有限公司 Silicon negative electrode material coated by double-layer coating layer and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113684471A (en) * 2021-08-02 2021-11-23 江苏鎏溪光学科技有限公司 System and method for monitoring reaction atmosphere in chemical vapor deposition process
CN114497484A (en) * 2022-01-04 2022-05-13 广东东岛新能源股份有限公司 Silica-based composite anode material and preparation method thereof

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