WO2016031085A1 - Matériau d'anode pour batterie au lithium-ion - Google Patents

Matériau d'anode pour batterie au lithium-ion Download PDF

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Publication number
WO2016031085A1
WO2016031085A1 PCT/JP2014/073423 JP2014073423W WO2016031085A1 WO 2016031085 A1 WO2016031085 A1 WO 2016031085A1 JP 2014073423 W JP2014073423 W JP 2014073423W WO 2016031085 A1 WO2016031085 A1 WO 2016031085A1
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WIPO (PCT)
Prior art keywords
anode material
lithium
active materials
ion battery
hard carbon
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PCT/JP2014/073423
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English (en)
Inventor
Qian CHENG
Noriyuki Tamura
Kentaro Nakahara
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Nec Corporation
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Publication date
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Priority to PCT/JP2014/073423 priority Critical patent/WO2016031085A1/fr
Priority to JP2017511959A priority patent/JP6384596B2/ja
Publication of WO2016031085A1 publication Critical patent/WO2016031085A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/02—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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

Definitions

  • the present invention relates to a negative electrode (anode) material for a lithium ion battery. Particularly, the present invention relates to a composite anode material of hard carbon and active particle.
  • LIBs lithium-ion batteries
  • lithium titanate is an alternative to graphite with good cycling properties, but it has a lower energy density.
  • these other alternatives for negative electrode materials have been found to be unsuitable commercially due to poor discharge and recharge cycling related to structural changes and anomalously large volume expansions, especially for silicon, that are associated with lithium intercalation/alloying. The structural changes and large volume changes can destroy the structural integrity of the electrode, thereby decreasing the cycling efficiency.
  • Li storable substance composite anode materials for example: JP 2004-119176 A, JP 2004-349253 A and JP 2005-71938 A. These disclose that Li storable substance such as Si, Sn and oxide thereof is embedded in carbon matrix.
  • the conventional composite anode materials are fabricated by previously manufacturing active materials that is Li storable substance and then coating the active material with carbon. Therefore, the content of the active material varies in each particle.
  • An object of the present invention is to provide an anode material for a lithium ion battery comprising active materials embedded hard carbon with less content variation of the active materials in each particle and a lithium ion battery including the anode materials.
  • one aspect of the present invention provides an anode material for a lithium-ion battery including active materials embedded in hard carbon, wherein the active materials includes oxide of at least one kind of metals selected from silicon and tin and the oxide is made from its precursor by solvothermal synthesis in a medium comprising a precursor of the hard carbon.
  • the active material since the active material is prepared in situ with carbon precursor decomposition, it can provide an anode material for a lithium ion battery comprising active materials embedded hard carbon with less content variation of the active materials in each particle.
  • Fig. 1 SEM image of anode material A manufactured in Example 1.
  • Fig. 2 XRD of anode material A manufactured in Example 1.
  • Fig. 3 SEM image of anode material B manufactured in Example 2.
  • An exemplary embodiment of the present invention relates to an anode material for the lithium ion battery including active materials embedded in hard carbon.
  • the anode material of the present exemplary embodiment is obtainable by solvothermal synthesis, particularly, hydrothermal synthesis employing water as a solvent.
  • a carbon precursor solution is provided by dissolving a carbon precursor in a solvent, such as water.
  • a precursor for an active material is added to the carbon precursor solution and then the mixture is heated under high pressure
  • the precursor for the active material is converted into the active material with a crystal form, particularly with a nano-crystal form.
  • the active material includes oxide of at least one kind of metals selected from silicon and tin.
  • the active material is usually silicon dioxide or tin dioxide, but they may include non-oxidized metal portions.
  • the carbon precursor is decomposed and adhered on the active material or an aggregate of the active materials.
  • decomposed carbon precursor is then carbonized at high temperature under inert atmosphere to convert into hard carbon.
  • the carbon precursor examples include polymers such as polyimides, furan resins, phenol resins, polyvinyl alcohols, cellulose resins, epoxy resins and polystyrene resins, and saccharides such as sucrose.
  • the carbon precursor is preferably soluble in water and saccharides are suitable.
  • the precursor for the active materials can be inorganic or organic compounds of silicon or tin.
  • the precursor for the active materials include inorganic or organic salts such as chlorides, sulfates, carbonates and the like of silicon and tin, organosilicon and organotin compounds such as 3-aminopropylmethyldiethoxysilane, butyl(trichloro)stannane.
  • the solvent used for solvothermal synthesis is a solvent that can dissolve the carbon precursor.
  • Water is preferably used and water-soluble solvents such as alcohols can be used with water.
  • the concentration of the carbon precursor solution is preferably in a range of
  • the solvothermal synthesis is conducted at a temperature less than the super-critical temperature of the solvent.
  • the hydrothermal synthesis is conducted at a temperature less than 374°C that is super-critical temperature of water, preferably in a range of 160 to 300°C for 1 to 24 hours.
  • the size of the anode material can be between 20 nm to 80 ⁇ , more preferably between 100 nm to 50 ⁇ , most preferably between 500 nm to 20 ⁇ .
  • the size of the active materials inside of the hard carbon can be less than 100 nm, preferably less than 50 nm, most preferably less than 10 nm.
  • the hard carbon can be doped with boron, nitrogen and the like. The ratio of the hard carbon to the active material is preferably 50:1 to 1 :1.
  • the active materials are prepared in situ with carbon precursor decomposition, the active materials are distributed in the hard carbon with atomic level uniform distribution. Therefore, it can reduce the content variation of the active materials in each particle.
  • Another exemplary embodiment relates to a lithium-ion battery including a negative electrode comprising the anode material according to the above exemplary embodiment.
  • the anode material preferably has a capacity of at least that of graphite, i.e., 372 niAh/g.
  • the battery also comprises a positive electrode comprising an active material, an electrolyte comprising a lithium salt dissolved in at least one non-aqueous solvent and a separator configured to allow electrolyte and lithium ions to flow between a first side of the separator and an opposite second side of the separator.
  • cathode materials can be used for practicing the present exemplary embodiment.
  • the cathode materials may be at least one material selected from the group consisting of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium-mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphates, metal sulfides, and combinations thereof.
  • the cathode material may also be at least one compound selected from chalcogenide compounds, such as titanium disulfate or molybdenum disulfate.
  • lithium cobalt oxide e.g., Li x Co0 2 where 0.8 ⁇ x ⁇ l
  • lithium nickel oxide e.g., LiNi0 2
  • lithium manganese oxide e.g., LiMn 2 0 4 and LiMn0 2
  • All these cathode materials can be prepared in the form of a fine powder, nano-wire, nano-rod, nano-fiber, or nano-tube. They can be readily mixed with an additional conductor such as acetylene black, carbon black, and ultra-fine graphite particles.
  • a binder For the preparation of the positive and negative electrodes, a binder can be used.
  • the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), ethylene propylenediene copolymer (EPDM), or styrene-butadiene rubber (SBR).
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • EPDM ethylene propylenediene copolymer
  • SBR styrene-butadiene rubber
  • the positive and negative electrodes can be formed on a current collector such as copper foil for the negative electrode and aluminum or nickel foil for the positive electrode. However, there is no particularly significant restriction on the type of the current collector, provided that the collector can smoothly path current and have relatively high corrosion resistance.
  • the positive and negative electrodes can be stacked with interposing a separator therebetween.
  • the separator can be selected from a synthetic resin nonwoven fabric, porous polyethylene film, porous polypropylene film, or porous PTFE film.
  • a wide range of electrolytes can be used for manufacturing the battery. Most preferred are non-aqueous and polymer gel electrolytes although other types of electrolytes can be used.
  • the non-aqueous electrolyte to be employed herein may be produced by dissolving an electrolyte salt (Li salt) in a non-aqueous solvent. Any known non-aqueous solvent which has been employed as a solvent for a lithium secondary battery can be employed.
  • a mixed solvent comprising ethylene carbonate (EC) and at least one kind of non-aqueous solvent whose melting point is lower than that of ethylene carbonate and whose donor number is 18 or less (hereinafter referred to as a second solvent) may be preferably employed as the non-aqueous solvent.
  • the second solvent to be used in the mixed solvent with EC functions to make the viscosity of the mixed solvent lowering than that of which EC is used alone, thereby improving an ion conductivity of the mixed solvent.
  • the second solvent having a donor number of 18 or less the donor number of ethylene carbonate is 16.4
  • the aforementioned ethylene carbonate can be easily and selectively solvated with lithium ion, so that the reduction reaction of the second solvent with the
  • the donor number of the second solvent is controlled to not more than 18, the oxidative decomposition potential to the lithium electrode can be easily increased to 4 V or more, so that it is possible to manufacture a lithium secondary battery of high voltage.
  • Preferable second solvents are dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), ⁇ - butyrolactone ( ⁇ -BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene and methyl acetate (MA).
  • DMC dimethyl carbonate
  • MEC methyl ethyl carbonate
  • DEC diethyl carbonate
  • ethyl propionate methyl propionate
  • PC propylene carbonate
  • ⁇ -BL ⁇ - butyrolactone
  • AN acetonitrile
  • EA ethyl acetate
  • PF propyl formate
  • MF methyl formate
  • MA toluene
  • MA methyl acetate
  • the viscosity of this second solvent should preferably be 28 cps or less at 25°C.
  • the mixing ratio of the aforementioned ethylene carbonate in the mixed solvent should preferably be 10 to 80% by volume. If the mixing ratio of the ethylene carbonate falls outside this range, the conductivity of the solvent may be lowered or the solvent tends to be more easily decomposed, thereby deteriorating the charge/discharge efficiency. More preferable mixing ratio of the ethylene carbonate is 20 to 75% by volume. When the mixing ratio of ethylene carbonate in a non-aqueous solvent is increased to 20% by volume or more, the solvating effect of ethylene carbonate to lithium ions will be facilitated and the solvent decomposition-inhibiting effect thereof can be improved.
  • additives may be added.
  • the SEI layer has a role to suppress reactivity with the electrolyte solution (decomposition), and subjected to desolvation reactions due to delithiation of the lithium ion battery, and to suppress the structural physical degradation of the anode material.
  • the additives include vinylene carbonate (VC), propane sultone (PS), and cyclic disulfonic acid ester.
  • Li salt according to this exemplary embodiment examples include LiPF 6 ,
  • the Li salt is not limited to these. One of these Li salts may be used, or two or more of these Li salts may be used in combination.
  • a casing for the battery in the exemplary embodiment may be, for example, a laminate film in which a substrate, a metal foil and a sealant are sequentially laminated.
  • a substrate which can be used include a resin film with a thickness of 10 to 25 ⁇ made of polyester (PET) or Nylon.
  • a metal foil may be an aluminum film with a thickness of 20 to 40 ⁇ .
  • a sealant may be a rein film with a thickness of 30 to 70 ⁇ made of polyethylene (PE), polypropylene (PP), modified polypropylene (PP) or an ionomer.
  • anode material A is a spherical particle having a smooth surface morphology.
  • Fig. 2 shows X-ray diffraction of anode material A.
  • the (110) face of Sn0 2 in anode material A shifted to higher incident angle (2 theta) compared with Sn0 2 synthesized by other methods, while other faces stayed on same incident angles.
  • an intensity ratio offace (110) to (101) of Sn0 2 in anode material A is higher than 1.1, where the intensity ratio of Sn0 2 synthesized by other methods is always less than 1.
  • the obtained powers were carbonized in an oven under N 2 atmosphere to obtain anode material B.
  • the carbonization was conducted at 100 ml/min of N 2 flow rate, 5°C/min of temperature raising rate and 1000°C of final temperature.
  • SEM images of anode material B are shown in Fig. 3.
  • silicon oxide is grown to rod-like crystals. Comparative example 1
  • Sn0 2 particles with average diameter of 10 ⁇ were used as anode material C.
  • SiO particles with average diameter of 5 ⁇ were used as anode material D.
  • Slurry was prepared by mixing each of anode materials A to D, carbon black, and PVDF in a weight ratio of 91 : 1 : 8 in N-methylpyrrolidone (NMP). The slurry was coated on a Cu foil and dried at 120°C for 15 min to form a thin substrate. Then, the thin substrate was pressed to 45 ⁇ thick with the loading density of 50 g/m 2 and then heat treated at 200°C for 2h in N 2 atmosphere to prepare a negative electrode.
  • NMP N-methylpyrrolidone
  • the negative electrode was used as a working electrode, while a metal lithium foil was used as a counter electrode.
  • a separator made of porous polypropylene film was interposed between the working electrode and counter electrode.
  • the electrolyte prepared by dissolving LiPF 6 in a mixed solvent of ethyl carbonate (DEC) and ethylene carbonate (EC) in a ratio of 7:3 in a concentration of 1M, then a laminate half-cell was fabricated.
  • test cell was evaluated in initial charge capacity, coulombic efficiency, rate capabilities of 1C charge/0.1C discharge and 6C charge/0.1C discharge and capacity retention 1C after 100 cycles. Results are shown in Table 1.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
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Abstract

La présente invention concerne un matériau d'anode pour une batterie au lithium-ion comprenant des matériaux actifs incorporés dans du carbone dur, les matériaux actifs comprenant un oxyde d'au moins un type de métaux choisis parmi le silicium et l'étain et l'oxyde étant constitué de son précurseur par synthèse solvothermale dans un milieu comprenant un précurseur du carbone dur.
PCT/JP2014/073423 2014-08-29 2014-08-29 Matériau d'anode pour batterie au lithium-ion WO2016031085A1 (fr)

Priority Applications (2)

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PCT/JP2014/073423 WO2016031085A1 (fr) 2014-08-29 2014-08-29 Matériau d'anode pour batterie au lithium-ion
JP2017511959A JP6384596B2 (ja) 2014-08-29 2014-08-29 リチウムイオン電池用アノード材料

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WO2017221882A1 (fr) * 2016-06-22 2017-12-28 Sharp Kabushiki Kaisha Matériau composite de carbone-métal/alliage, procédé de synthèse et électrode comprenant ce matériau
CN109148847A (zh) * 2018-08-07 2019-01-04 湖州创亚动力电池材料有限公司 一种具有高倍率性能的硼掺杂改性的硬碳包覆负极材料及其液相制备方法
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
CN112701265A (zh) * 2020-12-30 2021-04-23 桐乡市融杭科技合伙企业(有限合伙) 一种介孔碳包覆SnO2纳米花锂离子电池负极材料及制法
CN116799219A (zh) * 2023-08-25 2023-09-22 浙江华宇钠电新能源科技有限公司 一种锡基氧化物纳米晶修饰的硬碳、钠离子电池及车辆

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017221882A1 (fr) * 2016-06-22 2017-12-28 Sharp Kabushiki Kaisha Matériau composite de carbone-métal/alliage, procédé de synthèse et électrode comprenant ce matériau
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
CN109167025B (zh) * 2018-08-03 2021-04-09 湖州杉杉新能源科技有限公司 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
CN109148847A (zh) * 2018-08-07 2019-01-04 湖州创亚动力电池材料有限公司 一种具有高倍率性能的硼掺杂改性的硬碳包覆负极材料及其液相制备方法
CN109148847B (zh) * 2018-08-07 2021-04-09 湖州杉杉新能源科技有限公司 一种具有高倍率性能的硼掺杂改性的硬碳包覆负极材料及其液相制备方法
CN112701265A (zh) * 2020-12-30 2021-04-23 桐乡市融杭科技合伙企业(有限合伙) 一种介孔碳包覆SnO2纳米花锂离子电池负极材料及制法
CN116799219A (zh) * 2023-08-25 2023-09-22 浙江华宇钠电新能源科技有限公司 一种锡基氧化物纳米晶修饰的硬碳、钠离子电池及车辆
CN116799219B (zh) * 2023-08-25 2023-12-15 浙江华宇钠电新能源科技有限公司 一种锡基氧化物纳米晶修饰的硬碳、钠离子电池及车辆

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