CN116536629A - 一种中间相碳微球-硅碳复合材料及其制备方法 - Google Patents
一种中间相碳微球-硅碳复合材料及其制备方法 Download PDFInfo
- Publication number
- CN116536629A CN116536629A CN202310417287.7A CN202310417287A CN116536629A CN 116536629 A CN116536629 A CN 116536629A CN 202310417287 A CN202310417287 A CN 202310417287A CN 116536629 A CN116536629 A CN 116536629A
- Authority
- CN
- China
- Prior art keywords
- silicon
- composite material
- microsphere
- carbon microsphere
- mesophase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 98
- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004005 microsphere Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 12
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 10
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- 238000000151 deposition Methods 0.000 claims abstract description 5
- 238000007740 vapor deposition Methods 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 44
- 239000007789 gas Substances 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 24
- 229910052786 argon Inorganic materials 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000011159 matrix material Substances 0.000 claims description 13
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000013077 target material Substances 0.000 claims description 10
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- 238000004381 surface treatment Methods 0.000 claims description 4
- 238000005019 vapor deposition process Methods 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000002210 silicon-based material Substances 0.000 abstract description 17
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- -1 stirring and pulping Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005271 boronizing Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/223—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating specially adapted for coating particles
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C16/26—Deposition of carbon only
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C16/44—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 method of coating
- C23C16/4417—Methods specially adapted for coating powder
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明提供了一种中间相碳微球‑硅碳复合材料及其制备方法,所述方法的实现包括,对中间型碳微球进行表面处理,然后通过磁控溅射法在其表面沉积纳米硅,再通过气相沉积法沉积含有硼的碳源,得到所述中间相碳微球‑硅碳复合材料。本发明利用中间相碳微球的球形结构降低硅基材料的膨胀,及其掺杂硼的无定形碳降低阻抗;同时采用磁控溅射法实现精确控制纳米硅的沉积量及其均匀性,并结合气相沉积法在其外表面无定形碳,避免硅基材料与电解液直接接触,提升存储性能及其降低产气。其制备出的中间相碳微球‑硅碳复合材料具有膨胀低、首次效率高等特性。
Description
技术领域
本发明涉及锂离子电池材料制备技术领域,具体提供一种中间相碳微球-硅碳复合材料及其制备方法。
背景技术
锂离子电池是当今国际公认的理想化学能源,具有体积小、电容量大、电压高等优点,被广泛用于移动电话手提电脑等电子产品,日益扩大的电动汽车领域将给锂离子电池带来更大的发展空间。
锂离子电池的性能主要取决于所用电池内部材料的结构和性能。这些电池内部材料包括正极材料、负极材料、电解质和隔膜等。其中正、负极材料的选择和质量直接决定锂离子电池的性能与价格。因此廉价、高性能的正、负极材料的研究一直是锂离子电池行业发展的重点。通常负极材料一般选用碳材料,硅作为地壳中的元素,储量丰富,同时其具有很高的理论比容量(4200mAhg-1),使其成为石墨负极材料的替代材料之一。
硅基材料以其能量密度高、材料来源广泛而成为高能量密度锂离子电池的首选负极材料,但是其膨胀高造成其电池模组膨胀力大并降低其循环性能,因此为提升硅基材料在锂离子电池的应用范围,需要从降低硅基材料的膨胀方面进行改进。而降低硅基材料的膨胀措施很多:比如硅的纳米化、硅的晶粒尺寸降低、多孔硅、硅的包覆改性及其硅基材料与碳基材料的复合降低膨胀,上述措施虽然可以降低膨胀,但是会造成材料的其它性能恶化,比如高温存储、首次效率及其比容量等电性能下降。
发明内容
中间相碳微球以其各向同性,结构稳定等特性而应用于高倍率、长寿命、低膨胀锂离子电池,但是其比容量偏低影响其能量密度的提升。
因此本发明通过在中间相碳微球中掺杂硅基材料,不但可以提升能量密度而且可以降低膨胀。
为降低硅基材料的膨胀,本发明通过磁控溅射法在中间相碳微球表面沉积硅基材料并进行表面硼掺杂提升电子导电率和降低不可逆容量,制备出中间相碳微球-硅碳复合材料,降低膨胀,提升比容量和首次效率。
为实现上述发明目的,本发明提供了一种中间相碳微球-硅碳复合材料及其制备方法;
一方面,本发明提供了如下技术方案:
一种中间相碳微球-硅碳复合材料制备方法,所述方法的实现包括,对中间型碳微球进行表面处理,然后通过磁控溅射法在其表面沉积纳米硅,再通过气相沉积法沉积含有硼的碳源,得到所述中间相碳微球-硅碳复合材料。
更进一步的,所述中间型碳微球进行表面处理的过程包括内容如下:
将所述中间相碳微球转移到等离子反应腔内,在入口端和出口端分别设置等离子源,其中入口端的等离子源为氧气和氩气混合气,体积比1:1~10,出口端等离子源为氨气和氩气混合气混合气,体积比1:1~10,反应室入口端的温度保持在200℃,由所述入口端至所述出口出口端温度逐渐升高,温升速率10~20℃/min,出口端的温度保持在500℃,得到氮掺杂氧化中间相碳微球。
更进一步的,所述磁控溅射法的实现过程包括内容如下:
以纳米硅基材料为靶材,将所述氮掺杂氧化中间相碳微球转移到真空室中并作为基体,抽真空,压力控制到10-4~10-3pa;
将所述基体加热到100~200℃,将Ar气通入真空室,
将所述靶材对所述基体进行轰击,得到硅氮共掺杂氧化中间相碳微球。
更进一步的,所述气相沉积法的实现包括步骤如下:
将所述硅氮共掺杂氧化中间相碳微球通入三氯化硼混合气体,加热,保温,之后改通碳源气体,加热,保温,最后停止加热,降温,粉碎,得到硼掺杂无定形碳包覆的所述中间相碳微球-硅碳复合材料。
更进一步的,所述三氯化硼混合气体为三氯化硼和氩气的混合气体,三氯化硼和氩气的 体积比1:1~10,流量10~100ml/min。
更进一步的,所述碳源气体为甲烷、乙烷、乙烯、乙炔中的一种或多种的组合,流量10~100ml/min。
更进一步的,所述纳米硅基材料为纳米Si或纳米SiO。
更进一步的,所述方法在气相沉积过程中,在通入三氯化硼混合气体之前,首先通入惰性气体排除管内空气;气相沉积过程完成后,降温在氩气气氛下进行。
更进一步的,所述三氯化硼混合气体通入过程中,温度保持在300~500℃,保温0.5~2h;
所述碳源气体通入过程中,温度保持在700~1200℃,保温0.5~2h。
本发明另一方面,提供技术方案如下:
一种中间相碳微球-硅碳复合材料,所述中间相碳微球-硅碳复合材料上述任一方法制备。
与现有技术相比,本发明一种中间相碳微球-硅碳复合材料及其制备方法具有以下突出的有益效果:
1)通过磁控溅射法在改性中间相碳微球表面沉积硅基材料,一方面利用氮掺杂氧化中间相碳微球表面的羧基、羟基使其硅基材料容易沉积在其表面,具有结合力强等优点,避免硅基材料在中间相碳微球的脱落,提升稳定性。同时中间相碳微球表面的N掺杂,具有较高的电子传导能力和相对稳定的结构,显著提升了材料的循环性能,延长了使用寿命;同时磁控溅射方法,反应时间短,工艺简单,可以有效实现连续化生产。
2)通过气体表面改性,即三氯化硼表面改性掺杂硼并进行碳化,得到硼掺杂无定形碳包覆硅氮中间相碳微球,提升外层的电子导电率和降低不可逆容量,提升首次效率,并改善存储性能。
附图说明
图1是本发明制备出的一种中间相碳微球-硅碳复合材料的SEM图。
实施方式
下面将结合附图和实施例,对本发明作进一步详细说明。
实施例
步骤S1:
将中间相碳微球转移到等离子反应腔内,在入口端和出口端分别设置等离子源,入口端的离子源为氧气/氩气混合气(体积比1:5),出口端为氨气/氩气混合气混合气(体积比1:5),在反应室入口端的温度为200℃,由入口至出口温度不断升高,升温速率15℃/min,反应室出口端的温度为500℃,得到氮掺杂氧化中间相碳微球;
步骤S2:
采用磁控溅射法,以纳米Si为靶材,氮掺杂氧化中间相碳微球转移到真空室中并作为基体,抽真空到5*10-3pa,并加热基体到150℃,之后真空室通入Ar气,靶材对真空室的基体进行轰击,得到硅氮共掺杂氧化中间相碳微球;
步骤S3:
之后将硅氮共掺杂氧化中间相碳微球转移到管式炉中,首先通入氩气惰性气体排除管内空气,之后通入三氯化硼混合气体(体积比,三氯化硼:氩气=1:5,流量50ml/min),并加热到400℃保温1h,之后改通甲烷气体(流量50ml/min),并加热到950℃保温1h,最后停止加热,在氩气气氛下降温到室温、粉碎,得到硼掺杂无定形碳包覆中间相碳微球-硅碳复合材料。
实施例
步骤S1:
将中间相碳微球转移到等离子反应腔内,在入口端和出口端分别设置等离子源,入口端的离子源为氧气/氩气混合气(体积比1:1),出口端为氨气/氩气混合气混合气(体积比1:1),在反应室入口端的温度为200℃,由入口至出口温度不断升高,升温速率10℃/min,反应室出口端的温度为500℃,得到氮掺杂氧化中间相碳微球;
步骤S2:
采用磁控溅射法,以SiO为靶材,氮掺杂氧化中间相碳微球转移到真空室中并作为基体,抽真空到10-4pa,并加热基体到100℃,之后真空室通入Ar气,靶材对真空室的基体进行轰击,得到硅氮共掺杂氧化中间相碳微球;
步骤S3:
之后将硅氮共掺杂氧化中间相碳微球转移到管式炉中,首先通入氩气惰性气体排除管内空气,之后通入三氯化硼混合气体(体积比,三氯化硼:氩气=1:1,流量10ml/min),并加热到300℃保温2h,之后改通乙烯气体,并加热到800℃保温2h,最后停止加热,在氩气气氛下降温到室温、粉碎,得到硼掺杂无定形碳包覆中间相碳微球-硅碳复合材料。
实施例
步骤S1:
将中间相碳微球转移到等离子反应腔内,在入口端和出口端分别设置等离子源,入口端的离子源为氧气/氩气混合气(体积比1: 10),出口端为氨气/氩气混合气混合气(体积比1: 10),在反应室入口端的温度为200℃,由入口至出口温度不断升高,升温速率20℃/min,反应室出口端的温度为500℃,得到氮掺杂氧化中间相碳微球;
步骤S2:
采用磁控溅射法,以SiO为靶材,氮掺杂氧化中间相碳微球转移到真空室中并作为基体,抽真空到10-3pa,并加热基体到200℃,之后真空室通入Ar气,靶材对真空室的基体进行轰击,得到硅氮共掺杂氧化中间相碳微球;
步骤S3:
之后将硅氮共掺杂氧化中间相碳微球转移到管式炉中,首先通入氩气惰性气体排除管内空气,之后通入三氯化硼混合气体(体积比,三氯化硼:氩气=1:1),并加热到500℃保温0.5h,之后改通乙炔气体,并加热到700℃保温0.5h,最后停止加热,在氩气气氛下降温到室温、粉碎,得到硼掺杂无定形碳包覆中间相碳微球-硅碳复合材料。
对比例:
将100g中间相碳微球与5g沥青、1g苯胺混合均匀,之后在温度为400℃碳化1h,得到氮掺杂中间相碳微球。之后取50g SiO与30g氮掺杂中间相碳微球混合均匀,之后转移到管式炉中,首先通入氩气惰性气体排除管内空气,之后通甲烷气体(流量50ml/min),并加热到950℃保温1h,最后停止加热,在氩气气氛下降温到室温、粉碎,得到无定形碳包覆中间相碳微球-硅碳复合材料。
测试试验:
(1)形貌测试
对实施例1中的中间相碳微球-硅碳复合材料进行SEM测试,测试结果如图1所示。由图1可知,该材料呈现球状结构,大小分布均匀,颗粒粒径介于8-12μm之间。
(2)扣式电池测试
将实施例1-3及对比例中的中间相碳微球-硅碳复合材料作为锂离子电池负极材料组装成扣式电池,分别记为A1、A2、A3、B1。
具体制备方法为:在锂离子电池负极材料中添加粘结剂、导电剂及溶剂,进行搅拌制浆,涂覆在铜箔上,经过烘干、碾压制得负极片;所用粘结剂为LA132,导电剂为SP,溶剂为NMP,负极材料、SP、PVDF、NMP的用量比例为95g:1g:4g:220mL;电解液中LiPF6为电解质,体积比为1:1的EC和DEC的混合物为溶剂;金属锂片为对电极,隔膜采用聚丙烯(PP)膜。扣式电池装配在充氩气的手套箱中进行。电化学性能在武汉蓝电CT2001A型电池测试仪上进行,充放电电压范围为0.005V至2.0V,充放电速率为0.1C,并测试其循环性能(0.1C/0.1C,100周)。测试结果如表1所示。
表1
材料 | 首次放电比容量(mAH/g) | 首次效率(%) | 比表面积(m2/g) | 振实密度(g/cm3) | 粉体电导率(S/cm) | 循环性能 |
实施例1 | 998.4 | 86.9 | 7.5 | 1.09 | 2.81 | 92.1% |
实施例2 | 881.4 | 85.5 | 7.4 | 1.07 | 1.99 | 90.9% |
实施例3 | 868.9 | 85.3 | 6.7 | 1.05 | 1.85 | 90.4% |
对比例 | 842.4 | 83.1 | 3.7 | 0.85 | 0.65 | 87.3% |
由表1中的数据可以看出,本发明的实施例制备出的中间相碳微球-硅碳复合材料的比容量、首次效率、循环性能明显优于对比例1。其原因是:通过磁控溅射法可以均匀的将硅基材料沉积在中间相碳微球表面,且氮掺杂氧化中间相碳微球与硅基材料具有较好的结合力,降低阻抗提升材料的比容量发挥,并提升首次效率。
(3)软包电池测试:
将实施例1-3及对比例中的中间相碳微球-硅碳复合材料掺杂80%的人造石墨作为负极材料制得负极片,以NCM532为正极材料;电解液中LiPF6为电解质,体积比为1:1的EC和DEC的混合物为溶剂;以Celgard 2400膜为隔膜,制备出5Ah软包电池,标记为C1、C2、C3、D1。分别测试负极片的吸液保液能力、极片物理反弹率、循环性能、极片满电膨胀。
a.吸液能力测试
采用1mL的滴定管,并吸取电解液VmL,在极片表面滴加一滴,并进行计时,直至电解液吸收完毕,记下时间t,计算极片的吸液速度V/t。测试结果如表2所示。
b.保液率测试
按照极片参数计算出极片的理论吸液量m1,并称取极片的重量m2,之后将极片放置到电解液中浸泡24h,称取极片的重量为m3,计算出极片吸液量m3-m2,并按照下式计算:保液率=(m3-m2)*100%/m1。测试结果如表2所示。
表2
材料 | 吸液速度(S) | 保液率 |
实施例1 | 56 | 93.1% |
实施例2 | 65 | 92.0% |
实施例3 | 69 | 92.2% |
对比例1 | 121 | 84.7% |
从表2可以看出,实施例1-3所得中间相碳微球-硅碳复合材料的吸液保液能力明显高于对比例。实验结果表明,本发明的中间相碳微球-硅碳复合材料具有较高的吸液保液能力。其原因在于:实施例复合材料的比表面较大,提升材料的吸液保液能力。
c.极片物理反弹率测试
首先采用测厚仪测试其极片的平均厚度为D1,之后将极片放置在80度的真空干燥箱中干燥48h,测试极片的厚度为D2,并按下式计算:反弹率=(D2-D1)*100%/D1。测试结果如表3所示。
d.极片电阻率测试
采用电阻率测试仪测试极片的电阻率,测试结果如表3所示。
E.极片满电膨胀测试
对5Ah软包电池进行充电到100%SOC,之后解剖拆解,测试其负极极片的厚度为D3,同时测试其负极极片辊压的厚度为D1,并计算出负极极片的满电膨胀率=(D3-D1)/D1*100%。
表3
材料 | 极片物理反弹率(%) | 极片电阻率(mΩ) | 极片满电膨胀率(%) |
实施例1 | 7.8 | 15.8 | 34.8 |
实施例2 | 8.6 | 16.9 | 35.7 |
实施例3 | 9.1 | 17.1 | 36.9 |
对比例 | 15.6 | 218.5 | 42.8 |
从表3中数据可以看出,采用实施例1-3所得负极极片反弹率和电阻率明显低于对比例,即采用本发明的复合材料制得的负极片具有较低的反弹率和电阻率。其原因在于:采用磁控溅射法可以将硅基材料致密的沉积在中间相碳微球的表面或内部,使其材料之间的接触较好,反弹更低。
f.循环性能测试
以充放电倍率为1C/1C、电压范围为2.5V-4.2V,在温度25±3℃下测试电池的循环性能。测试结果如表4所示。
表4
电池 | 负极材料 | 循环500次容量保持率(%) |
C1 | 实施例1 | 92.60 |
C2 | 实施例2 | 91.72 |
C3 | 实施例3 | 90.31 |
D1 | 对比例 | 85.52 |
由表4可以看出,本发明的中间相碳微球-硅碳复合材料制得的电池的循环性能明显优于对比例,其原因为,本发明的中间相碳微球-硅碳复合材料制得的极片具有较低的膨胀率,在充放电过程中极片的结构更加稳定,提高了其循环性能;另外通过掺杂硼降低阻抗,提升材料的结构稳定性,并改善循环性能。
将碳源气体更换为乙烷或甲烷、乙烷、乙烯、乙炔中的一种或多种的组合,制得的硅基复合负极材料性能相近。
以上所述的实施例,只是本发明较优选的具体实施方式,本领域的技术人员在本发明技术方案范围内进行的通常变化和替换都应包含在本发明的保护范围内。
Claims (10)
1.一种中间相碳微球-硅碳复合材料制备方法,其特征在于,所述方法的实现包括,对中间型碳微球进行表面处理,然后通过磁控溅射法在其表面沉积纳米硅,再通过气相沉积法沉积含有硼的碳源,得到所述中间相碳微球-硅碳复合材料。
2.根据权利要求1所述的一种中间相碳微球-硅碳复合材料制备方法,其特征在于,所述中间型碳微球进行表面处理的过程包括内容如下:
将所述中间相碳微球转移到等离子反应腔内,在入口端和出口端分别设置等离子源,其中入口端的等离子源为氧气和氩气混合气,体积比1:1~10,出口端等离子源为氨气和氩气混合气混合气,体积比1:1~10,反应室入口端的温度保持在200℃,由所述入口端至所述出口出口端温度逐渐升高,温升速率10~20℃/min,出口端的温度保持在500℃,得到氮掺杂氧化中间相碳微球。
3.根据权利要求2所述的一种中间相碳微球-硅碳复合材料制备方法,其特征在于,所述磁控溅射法的实现过程包括内容如下:
以纳米硅基材料为靶材,将所述氮掺杂氧化中间相碳微球转移到真空室中并作为基体,抽真空,压力控制到10-4~10-3pa;
将所述基体加热到100~200℃,将Ar气通入真空室,
将所述靶材对所述基体进行轰击,得到硅氮共掺杂氧化中间相碳微球。
4.根据权利要求3所述的一种中间相碳微球-硅碳复合材料制备方法,其特征在于,所述气相沉积法的实现包括步骤如下:
将所述硅氮共掺杂氧化中间相碳微球通入三氯化硼混合气体,加热,保温,之后改通碳源气体,加热,保温,最后停止加热,降温,粉碎,得到硼掺杂无定形碳包覆的所述中间相碳微球-硅碳复合材料。
5.根据权利要求4所述的一种中间相碳微球-硅碳复合材料制备方法,其特征在于,所述三氯化硼混合气体为三氯化硼和氩气的混合气体,三氯化硼和氩气的体积比1:1~10,流量10~100ml/min。
6.根据权利要求4所述的一种中间相碳微球-硅碳复合材料制备方法,其特征在于,所述碳源气体为甲烷、乙烷、乙烯、乙炔中的一种或多种的组合,流量10~100ml/min。
7.根据权利要求3所述的一种中间相碳微球-硅碳复合材料制备方法,其特征在于,所述纳米硅基材料为纳米Si或纳米SiO。
8.根据权利要求4所述的一种中间相碳微球-硅碳复合材料制备方法,其特征在于,所述方法在气相沉积过程中,在通入三氯化硼混合气体之前,首先通入惰性气体排除管内空气;气相沉积过程完成后,降温在氩气气氛下进行。
9.根据权利要求4或8所述的一种中间相碳微球-硅碳复合材料制备方法,其特征在于,所述三氯化硼混合气体通入过程中,温度保持在300~500℃,保温0.5~2h;
所述碳源气体通入过程中,温度保持在700~1200℃,保温0.5~2h。
10.一种中间相碳微球-硅碳复合材料,其特征在于,所述中间相碳微球-硅碳复合材料基于权利要求1-9任一方法制备。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310417287.7A CN116536629B (zh) | 2023-04-19 | 2023-04-19 | 一种中间相碳微球-硅碳复合材料及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310417287.7A CN116536629B (zh) | 2023-04-19 | 2023-04-19 | 一种中间相碳微球-硅碳复合材料及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN116536629A true CN116536629A (zh) | 2023-08-04 |
CN116536629B CN116536629B (zh) | 2024-03-19 |
Family
ID=87451508
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310417287.7A Active CN116536629B (zh) | 2023-04-19 | 2023-04-19 | 一种中间相碳微球-硅碳复合材料及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116536629B (zh) |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108117056A (zh) * | 2017-12-11 | 2018-06-05 | 上海交通大学 | 石墨烯包覆等离子体改性中间相碳微球的制备方法 |
CN109167025A (zh) * | 2018-08-03 | 2019-01-08 | 湖州创亚动力电池材料有限公司 | 一种高低温环境下具有高稳定性的硼掺杂改性的软碳包覆负极材料及其制备方法 |
CN109216689A (zh) * | 2018-10-25 | 2019-01-15 | 湖北融通高科先进材料有限公司 | 一种硅碳复合材料及其制备方法和锂离子电池 |
US20190280301A1 (en) * | 2018-03-07 | 2019-09-12 | Nanotek Instruments, Inc. | Method of producing electrochemically stable elastomer-encapsulated particles of anode active materials for lithium batteries |
US20190355980A1 (en) * | 2018-05-16 | 2019-11-21 | Ph Matter, Llc | Energy storage material and method of producing the same |
CN111653727A (zh) * | 2020-06-30 | 2020-09-11 | 陕西煤业化工技术研究院有限责任公司 | 一种预锂化硅基薄膜负极材料及其制备方法 |
WO2022156152A1 (zh) * | 2021-01-20 | 2022-07-28 | 惠州市豪鹏科技有限公司 | 硅复合材料及其制备方法、负极片和锂离子电池 |
WO2022166007A1 (zh) * | 2021-02-02 | 2022-08-11 | 广东凯金新能源科技股份有限公司 | 一种三维碳硅复合材料及其制备方法 |
CN115188949A (zh) * | 2022-07-22 | 2022-10-14 | 晖阳(贵州)新能源材料有限公司 | 一种中间相碳微球-硅碳复合负极材料的制备方法 |
CN115207326A (zh) * | 2022-08-16 | 2022-10-18 | 四川坤天新能源科技有限公司 | 一种低膨胀硅碳复合材料及其制备方法 |
CN115207329A (zh) * | 2022-08-25 | 2022-10-18 | 四川坤天新能源科技有限公司 | 一种高能量密度硅碳/中间相碳微球复合材料的制备方法 |
CN115458725A (zh) * | 2022-10-14 | 2022-12-09 | 中国石油大学(华东) | 一种中间相炭微球基硅碳复合电极材料的改性制备方法 |
-
2023
- 2023-04-19 CN CN202310417287.7A patent/CN116536629B/zh active Active
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108117056A (zh) * | 2017-12-11 | 2018-06-05 | 上海交通大学 | 石墨烯包覆等离子体改性中间相碳微球的制备方法 |
US20190280301A1 (en) * | 2018-03-07 | 2019-09-12 | Nanotek Instruments, Inc. | Method of producing electrochemically stable elastomer-encapsulated particles of anode active materials for lithium batteries |
US20190355980A1 (en) * | 2018-05-16 | 2019-11-21 | Ph Matter, Llc | Energy storage material and method of producing the same |
CN109167025A (zh) * | 2018-08-03 | 2019-01-08 | 湖州创亚动力电池材料有限公司 | 一种高低温环境下具有高稳定性的硼掺杂改性的软碳包覆负极材料及其制备方法 |
CN109216689A (zh) * | 2018-10-25 | 2019-01-15 | 湖北融通高科先进材料有限公司 | 一种硅碳复合材料及其制备方法和锂离子电池 |
CN111653727A (zh) * | 2020-06-30 | 2020-09-11 | 陕西煤业化工技术研究院有限责任公司 | 一种预锂化硅基薄膜负极材料及其制备方法 |
WO2022156152A1 (zh) * | 2021-01-20 | 2022-07-28 | 惠州市豪鹏科技有限公司 | 硅复合材料及其制备方法、负极片和锂离子电池 |
WO2022166007A1 (zh) * | 2021-02-02 | 2022-08-11 | 广东凯金新能源科技股份有限公司 | 一种三维碳硅复合材料及其制备方法 |
CN115188949A (zh) * | 2022-07-22 | 2022-10-14 | 晖阳(贵州)新能源材料有限公司 | 一种中间相碳微球-硅碳复合负极材料的制备方法 |
CN115207326A (zh) * | 2022-08-16 | 2022-10-18 | 四川坤天新能源科技有限公司 | 一种低膨胀硅碳复合材料及其制备方法 |
CN115207329A (zh) * | 2022-08-25 | 2022-10-18 | 四川坤天新能源科技有限公司 | 一种高能量密度硅碳/中间相碳微球复合材料的制备方法 |
CN115458725A (zh) * | 2022-10-14 | 2022-12-09 | 中国石油大学(华东) | 一种中间相炭微球基硅碳复合电极材料的改性制备方法 |
Non-Patent Citations (5)
Title |
---|
YANGFAN LIN: "Wet-chemical synthesized MCMB@Si@C microspheres for high-performance lithium-ion battery anodes", 《CHEMICAL COMMUNICATIONS》, vol. 54, no. 68, pages 9466 - 9468 * |
张瑛洁;刘洪兵;: "化学气相沉积法制备Si/C复合负极材料的研究进展", 硅酸盐通报, no. 1, pages 7 - 11 * |
李同起, 王成扬: "中间相炭微球研究进展", 炭素技术, no. 03, pages 24 - 29 * |
赵圣雷: "锂电负极材料中间相炭微球的应用研究进展", 《炭素》, no. 1, pages 39 - 43 * |
黄玥等: "锂离子电池硅碳复合负极材料结构设计与研究进展", 《应用化学》, vol. 49, no. 1, pages 185 - 189 * |
Also Published As
Publication number | Publication date |
---|---|
CN116536629B (zh) | 2024-03-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112133896B (zh) | 一种高容量石墨-硅-氧化亚硅复合材料及其制备方法、应用 | |
CN114122357B (zh) | 一种锂盐包覆石墨烯掺杂硅碳复合材料及其制备方法 | |
CN115566170B (zh) | 一种高能量密度快充锂离子电池负极材料的制备方法 | |
CN115566167A (zh) | 一种气态雾化法制备硅基复合材料及制备方法 | |
CN116314722A (zh) | 一种氟氮掺杂无定形碳包覆硅碳复合材料及其制备方法 | |
CN115692677A (zh) | 一种高功率低膨胀硅氧金属氧化物复合材料及其制备方法 | |
CN115207326A (zh) | 一种低膨胀硅碳复合材料及其制备方法 | |
CN110474037B (zh) | 一种多孔硅碳复合负极材料的制备方法 | |
CN109301224B (zh) | 一种锂离子电池硅基复合负极材料的制备方法及应用 | |
CN114583137B (zh) | 一种在碳表面进行硫掺杂磷修饰的方法及其应用 | |
CN116536629B (zh) | 一种中间相碳微球-硅碳复合材料及其制备方法 | |
CN114122392B (zh) | 一种高容量快充石墨复合材料及其制备方法 | |
CN114975974A (zh) | 一种高能量密度石墨复合材料及其制备方法、锂离子电池 | |
CN112421002B (zh) | 一种高容量的硅碳材料及其制备方法 | |
CN114864897A (zh) | 一种快充的石墨复合材料及其制备方法 | |
CN109860527B (zh) | 一种制备锂电池负极的碳基复合材料及其制备方法 | |
CN113206213A (zh) | 一种硅基复合电极及其制备方法和应用 | |
CN111925232A (zh) | 一种石墨表面硅/碳双层包覆的负极材料及其制备方法 | |
CN115332496B (zh) | 一种锂离子电池所用硅氧复合材料的制备方法 | |
CN116314671B (zh) | 一种硅碳复合材料的制备方法和硅碳复合材料 | |
CN116314806A (zh) | 一种多孔硅氧复合负极材料及其制备方法 | |
CN114725361B (zh) | 一种含铁氧化物包覆硫掺杂膨胀石墨/硅电极材料及其制备方法 | |
CN115893400B (zh) | 一种长循环锂离子电池所用负极材料的制备方法 | |
US20240178371A1 (en) | Silicon-based anode material with high stability and conductivity for lithium-ion batteries and preparation method thereof | |
CN116525805A (zh) | 一种高功率硅基复合负极材料及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |