WO2023108458A1 - Aluminum-based amorphous negative electrode active material, composite negative electrode active material, battery negative electrode material, and battery - Google Patents

Aluminum-based amorphous negative electrode active material, composite negative electrode active material, battery negative electrode material, and battery Download PDF

Info

Publication number
WO2023108458A1
WO2023108458A1 PCT/CN2021/138187 CN2021138187W WO2023108458A1 WO 2023108458 A1 WO2023108458 A1 WO 2023108458A1 CN 2021138187 W CN2021138187 W CN 2021138187W WO 2023108458 A1 WO2023108458 A1 WO 2023108458A1
Authority
WO
WIPO (PCT)
Prior art keywords
negative electrode
active material
electrode active
aluminum
based amorphous
Prior art date
Application number
PCT/CN2021/138187
Other languages
French (fr)
Chinese (zh)
Inventor
蒋春磊
唐永炳
王豆丰
石磊
Original Assignee
深圳先进技术研究院
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 深圳先进技术研究院 filed Critical 深圳先进技术研究院
Priority to PCT/CN2021/138187 priority Critical patent/WO2023108458A1/en
Publication of WO2023108458A1 publication Critical patent/WO2023108458A1/en

Links

Images

Classifications

    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • 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
    • 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
    • H01M4/46—Alloys based on magnesium or aluminium
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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
    • 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 invention relates to the technical field of energy storage materials, in particular to an aluminum-based amorphous negative electrode active material, a composite negative electrode active material, a battery negative electrode material and a battery.
  • lithium-ion batteries Due to its high energy density, high operating voltage and good cycle stability, lithium-ion batteries have been widely used in various consumer electronics products, power tools, electric vehicles, and energy storage.
  • most of the current commercial lithium-ion battery anodes use graphite as the anode active material, and the theoretical capacity is limited (372mAh/g), which makes it difficult to meet the performance requirements of high energy density and long battery life. Therefore, the development of new anode materials with high capacity has become an important research direction for lithium-ion batteries.
  • Alloyed negative electrode has high theoretical capacity, such as silicon has a theoretical capacity of up to 4200mAh/g, tin has a theoretical capacity of up to 994mAh/g, and aluminum has a theoretical capacity of up to 2234mAh/g.
  • alloy-based anode materials produce large anisotropic volume changes during the alloying reaction process, resulting in cracking and pulverization, which seriously affects the cycle stability of the battery.
  • amorphous materials have isotropic volume change characteristics, which can significantly reduce stress concentration, and at the same time, the microstructure is relatively loose, which can alleviate volume expansion. Therefore, amorphization treatment is one of the effective means to improve the structural stability of alloyed anode materials.
  • the prior art also records a silicon-containing porous amorphous alloy lithium-ion battery negative electrode material and its preparation method.
  • the negative electrode material mainly contains Si, Fe, B and other elements, and the Si content is 10-60 at%.
  • the content is 10-35at%, the content of Fe is 0-55at%, and the content of other elements is the balance; its preparation method is to add Si-containing Fe-based amorphous alloy or amorphous nanocrystalline composite material to dilute hydrochloric acid to corrode and remove Fe and then, standing still, suction filtering, washing, drying, ultrasonic pulverization and sieving to obtain a silicon-containing porous amorphous alloy material.
  • silicon-based amorphous material has a good effect on improving its structural stability.
  • silicon itself is a poor conductor of electrons, with poor electrical conductivity, low battery charge transfer efficiency, and low rate capability;
  • the volume expansion is still very large ( ⁇ 300%), and the pole piece needs to reserve enough buffer space, resulting in low volume energy density, or causing the pole piece to crack and fail.
  • the object of the present invention is to provide an aluminum-based amorphous negative electrode active material, composite negative electrode active material, battery negative electrode material and battery to solve the problems of low specific capacity of traditional graphite negative electrodes, severe expansion and pulverization of alloy negative electrodes, and poor cycle performance.
  • the present invention provides the following technical solutions:
  • the first aspect of the present invention provides an aluminum-based amorphous negative electrode active material, which includes aluminum elements and modified metal elements, and the modified metal elements include rare earth elements and/or transition metal elements.
  • the content of aluminum elements is 50% to 90%, the content of rare earth elements is 0% to 10%, and the content of transition metal elements is 0% to 50%.
  • the sum of the contents of metal elements is greater than 0;
  • the content of transition metal elements is greater than 0, and the content of rare earth elements is greater than 0;
  • the content of the aluminum element is 80%-90%, and the content of the transition metal element is greater than 0 and less than or equal to 20%.
  • the rare earth elements include one or more of yttrium, dysprosium, and ytterbium
  • the transition metal elements include one or more of titanium, iron, and nickel.
  • the preparation method of the aluminum-based amorphous negative electrode active material includes a mechanical ball milling method, a vapor deposition method or a rapid cooling method.
  • the second aspect of the present invention provides a composite negative electrode active material, the composite negative electrode active material is obtained by compounding the aluminum-based amorphous negative electrode active material provided by the first aspect of the present invention, including graphite materials and the aluminum-based amorphous negative electrode active material .
  • the graphite-based materials include natural graphite, artificial graphite, three-dimensional graphite sponge, mesocarbon microspheres (MCMB), soft carbon, hard carbon, pyrolytic carbon, petroleum coke, coke, and graphene.
  • MCMB mesocarbon microspheres
  • the graphite-based material and the aluminum-based amorphous negative electrode active material are composited by a mechanical mixing method, a vapor deposition method or a hydrothermal synthesis method.
  • the third aspect of the present invention provides a battery negative electrode material, including a negative electrode active material, a conductive agent and a binder, and the negative electrode active material is the aluminum-based amorphous negative electrode active material provided by the first aspect of the present invention or the second aspect of the present invention Provided composite negative electrode active materials.
  • the fourth aspect of the present invention provides a battery negative electrode, including a current collector and the battery negative electrode material provided by the third aspect of the present invention.
  • the fifth aspect of the present invention provides a battery, including the negative electrode of the battery provided by the fourth aspect of the present invention.
  • the battery provided by the fifth aspect of the present invention is an energy storage device such as a half battery such as a button battery, a full battery such as a lithium ion battery, a supercapacitor, or a hybrid supercapacitor.
  • the beneficial effects of the present invention are: the aluminum-based amorphous negative electrode active material and the composite negative electrode active material provided by the present invention have small volume change on the one hand, and have isotropic volume change characteristics, which can effectively suppress stress
  • the relatively loose microstructure can effectively alleviate the volume expansion, thereby significantly improving the structural stability
  • the composite negative electrode active material of the composite graphite material can effectively alleviate the volume expansion than the aluminum-based amorphous negative electrode active material
  • Aluminum-based materials have good electrical conductivity, which can effectively improve the charge transport efficiency and improve the rate performance.
  • Fig. 1 is the selected area electron diffraction pattern of the Al 83 Ti 10 Y 7 amorphous sample prepared in Example 1;
  • Fig. 2 is the cycle performance diagram of the aluminum-based amorphous composite negative electrode half-cell prepared in Example 3;
  • Fig. 3 is a cycle performance diagram of a lithium-ion full battery combined with an aluminum-based amorphous composite negative electrode prepared in Example 106.
  • the conductive agent described in the negative electrode material of the present invention is not limited in any way, and commonly used conductive additives in the field such as acetylene black, conductive carbon black, and graphite are used to improve the conductivity of electrons generated in the electrode and improve battery performance.
  • the binder described in the negative electrode material of the present invention is without any limitation, can enumerate styrene-butadiene rubber (SBR) emulsion, carboxymethyl cellulose (CMC), polyethylene oxide (PEO), polypropylene oxide (PPO) ), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polyacrylonitrile (PAN), polymethyl acrylate (PMA), polymethyl methacrylate (PMMA) and other examples.
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • PEO polyethylene oxide
  • PPO polypropylene oxide
  • PVDF polyvinylidene fluoride
  • PVDF-HFP polyvinylidene fluoride-hexafluoropropylene copolymer
  • PAN polyacrylonitrile
  • PMA polymethyl acrylate
  • the current collector described in the negative electrode of the present invention is an inactive conductive current collector, without any limitation, copper foil (net), titanium foil (net), iron foil (net), nickel foil (net), carbon cloth, Examples of conductive nylon and the like, but not limited to the above materials.
  • the electrolyte solution in the assembled battery of the present invention is not limited, the electrolyte salt can be exemplified by LiPF 6 , LiBF 4 , LiFSI, LiTFSI, etc., and the solvent is one or more of esters, sulfones, ethers, nitriles, and olefins.
  • a preferred solvent is a single solvent or a combination of solvents such as ethylene carbonate (EC), ethyl methyl carbonate (EMC), propylene carbonate (PC), dimethyl carbonate (DMC), and diethyl carbonate (DEC).
  • the separator used in the assembled battery of the present invention is not limited, and is an insulating porous polymer film or an inorganic porous film etc. conventionally used in the art, such as porous polypropylene film, porous polyethylene film, porous composite polymer film, insulating fiber paper Or a porous ceramic diaphragm, preferably an insulating fiber diaphragm, such as a glass fiber diaphragm.
  • the negative electrode provided by the present invention can be used for energy storage devices such as half batteries such as button batteries, full batteries such as lithium ion batteries, supercapacitors, and hybrid supercapacitors.
  • energy storage devices such as half batteries such as button batteries, full batteries such as lithium ion batteries, supercapacitors, and hybrid supercapacitors.
  • Example 1 Preparation of an amorphous negative electrode active material based on Al 83 Ti 10 Y 7
  • Figure 1 is the selected area electron diffraction pattern of the prepared Al 83 Ti 10 Y 7 amorphous sample. It can be seen from Figure 1 that the Al 83 Ti 10 Y 7 powder has an amorphous structure.
  • the negative electrode select copper foil as the inactive conductive current collector, select glass fiber as the diaphragm, and prepare the negative electrode: (1) use copper foil as the base material, and use absolute ethanol to clean its surface for later use; (2) prepare the non- Crystalline Al 83 Ti 10 Y 7 powder is used as the negative electrode active material, conductive carbon black is used as the conductive agent, and the binder CMC is uniformly mixed according to the mass ratio of 8:1:1, and then N-methylpyrrolidone (NMP) solvent is added for thorough stirring to obtain Slurry, the slurry is uniformly coated on the surface of the clean copper foil obtained in step (1), and then placed in a vacuum oven for drying treatment at a temperature of 80° C. for 24 hours to obtain a negative electrode sheet.
  • NMP N-methylpyrrolidone
  • Assemble the battery add LiPF 6 electrolyte salt to the mixed solvent of EC and DEC (volume ratio 1:1), then fully stir and dissolve to obtain the electrolyte; in a glove box filled with Ar, and the content of H 2 O and O 2 Under the condition of ⁇ 0.1ppm, the negative pole piece, the glass fiber separator, and the lithium foil of the counter electrode were stacked in sequence, and the electrolyte solution was added to assemble a coin cell for a half-cell performance test. The test results are shown in Table 1.
  • Example 2 Preparation of an amorphous negative electrode active material based on Al 83 Ti 10 Y 7
  • Example 1 The only difference from Example 1 is that vapor deposition is used to directly deposit aluminum-based amorphous negative electrode active materials on the surface of the current collector.
  • the specific operation is: use a composite sputtering target of Al, Ti and Y to deposit aluminum-based An amorphous negative electrode active material is obtained to obtain a negative electrode sheet.
  • the button battery was assembled according to the same method as in Example 1 to perform a half-cell performance test, and the test results are shown in Table 1.
  • Example 3 Preparation of a composite negative electrode active material based on Al 83 Ti 10 Y 7
  • NMP N-methylpyrrolidone
  • NMP N-methylpyrrolidone
  • the N-methylpyrrolidone (NMP) solvent is fully stirred to obtain a slurry; the slurry is evenly coated on the surface of the aluminum-based amorphous/copper foil composite material obtained in step (2) to obtain graphite/aluminum-based amorphous/
  • the copper foil composite material is the composite negative electrode active material coated on the surface of the copper foil.
  • Preparation of negative electrode Put the graphite/aluminum-based amorphous/copper foil composite material prepared above into a vacuum oven for drying treatment at a temperature of 80° C. for 24 hours to obtain a negative electrode sheet.
  • Assemble the battery add LiPF 6 electrolyte salt to the mixed solvent of EC and DEC (volume ratio 1:1), then fully stir and dissolve to obtain the electrolyte; in a glove box filled with Ar, and the content of H 2 O and O 2 Under the condition of ⁇ 0.1ppm, the negative electrode sheet, the glass fiber separator, and the lithium foil of the counter electrode were stacked in sequence, and the electrolyte was filled to assemble a button cell for half-cell performance testing.
  • the cycle performance diagram is shown in Figure 2.
  • Example 4 Preparation of a composite negative electrode active material based on Al 83 Ti 10 Y 7
  • step (2) and step (3) are exchanged, that is, graphite/copper foil composite material is obtained first, and then amorphous Al 83 Ti 10 Y 7 powder, conductive carbon black and binder CMC
  • the slurry prepared by mixing according to the same proportion is evenly coated on the surface of the graphite/copper foil composite material.
  • Example 3 According to the same method as in Example 3, the negative electrode was prepared, the button cell was assembled, and the half-cell performance test was carried out. The test results are shown in Table 1.
  • Example 5-86 Preparation of other aluminum-based amorphous composite negative electrode active materials
  • Example 3 The difference between Examples 5-86 and Example 3 is that different transition metal elements and rare earth elements are used, as shown in Table 1 below.
  • Table 1 The preparation of the negative electrode and the assembly of the button cell were the same as in Example 3.
  • Example 2 Using pure aluminum as the negative electrode active material, the same method as in Example 1 was used to prepare the negative electrode and assemble the battery.
  • Example 2 Using natural graphite as the negative electrode active material, the same method as in Example 1 was used to prepare the negative electrode and assemble the battery.
  • Example 87 The only difference between Example 87 and Example 3 is that different inactive conductive current collectors are used. Copper foil (network), titanium foil (network), iron foil (network), nickel foil (network), carbon cloth, and conductive nylon were used as inactive conductive current collectors, and the negative electrode was prepared and assembled in the same way as in Example 3. Button Battery.
  • Example 88-91 The difference between Examples 88-91 and Example 3 is that different diaphragm materials are used.
  • the same method as in Example 3 was used to prepare the negative electrode and assemble the button battery, and the electrochemical performance of the button battery was tested by the same method, as shown in Table 2 below.
  • Embodiment 92-97 The difference between Embodiment 92-97 and Embodiment 3 is that different graphite materials are used.
  • the same method as in Example 3 was used to prepare the negative electrode and assemble the button battery, and the electrochemical performance of the button battery was tested by the same method, as shown in Table 3 below.
  • Example 98 The difference between Example 98 and Example 3 is that the aluminum-based amorphous material and graphite-based material are compounded by ball milling.
  • the specific operation is:
  • step (2) Add the amorphous Al 83 Ti 10 Y 7 powder that step (2) obtains in natural graphite, conductive agent conductive carbon black, binding agent CMC, wherein mass ratio is (natural graphite and amorphous Al 83 Ti 10 Y
  • conductive agent: binder 8:1:1
  • NMP N-methylpyrrolidone
  • step (3) Evenly coat the slurry in step (3) on the surface of the copper foil obtained in step (1), and then put it into a vacuum oven for drying treatment at a temperature of 80° C. for 24 hours to obtain a negative electrode sheet.
  • Example 99 The difference between Example 99 and Example 3 is that the aluminum-based amorphous material is prepared by vapor deposition, and then compounded with graphite-based materials.
  • the specific operation is:
  • NMP N-methylpyrrolidone
  • step (3) Put the graphite/aluminum-based amorphous/conductive current collector composite material obtained in step (3) into a vacuum oven for drying treatment at a temperature of 80° C. for 24 hours to obtain a negative electrode sheet.
  • Example 100 The difference between Example 100 and Example 99 is that different composite processes are used to composite aluminum-based amorphous materials and graphite materials, and the specific operations are as follows:
  • the graphite active material prepared in step (1) is put into a vapor deposition furnace, and Al, Ti composite and Y are used as sputtering targets, and a layer of graphite active material is deposited on the surface of the graphite active material particles by vapor deposition.
  • the aluminum-based amorphous active material is used to obtain a graphite-based active material with an aluminum-based amorphous coating layer, that is, a composite negative electrode active material is obtained.
  • NMP N-methylpyrrolidone
  • Assemble the battery add LiPF 6 electrolyte salt to the mixed solvent of EC and DEC (volume ratio 1:1), then fully stir and dissolve to obtain the electrolyte; in a glove box filled with Ar, and the content of H 2 O and O 2 Under the condition of ⁇ 0.1ppm, the negative electrode sheet, the glass fiber separator, and the lithium foil of the counter electrode were stacked in sequence, and the electrolyte was filled to assemble a button battery for half-cell performance testing.
  • the initial discharge specific capacity was 435mAh/g, and the reversible discharge ratio The capacity is 421mAh/g, the number of cycles is 600, the final discharge capacity is 352mAh/g, and the capacity retention rate is 81%.
  • Example 101 The only difference between Examples 102-105 and Example 101 is that the positive electrode active material is different.
  • the aluminum-based amorphous composite negative electrode prepared in Example 3 of the present invention is used to construct a lithium-ion full battery, wherein the positive electrode active material is expanded graphite, the separator is preferably a glass fiber separator, and the electrolyte is 4M LiPF 6 /EMC+2% VC, assembled into a button battery. Concrete preparation steps are as follows:
  • Example 101 The difference between Examples 107-110 and Example 101 is that the electrolyte solution is different.

Abstract

The present invention relates to an aluminum-based amorphous negative electrode active material, a composite negative electrode active material, a battery negative electrode material, and a battery in the technical field of energy storage materials. The aluminum-based amorphous negative electrode active material comprises an aluminum element and a modified metal element, the modified metal element comprising a rare earth element and/or a transition metal element. On one hand, the aluminum-based amorphous negative electrode active material and the composite negative electrode active material provided by the present invention are small in volume change, and have isotropic volume change characteristics, and can effectively suppress stress concentration, and in addition, volume expansion can be effectively relieved by means of a loose microstructure, such that the structural stability is remarkably improved; on the other hand, the aluminum-based material has good conductivity, such that the charge transmission efficiency can be effectively improved, and the rate performance is improved.

Description

铝基非晶负极活性材料、复合负极活性材料、电池负极材料和电池Aluminum-based amorphous negative electrode active material, composite negative electrode active material, battery negative electrode material and battery 技术领域technical field
本发明涉及储能材料技术领域，具体是一种铝基非晶负极活性材料、复合负极活性材料、电池负极材料和电池。The invention relates to the technical field of energy storage materials, in particular to an aluminum-based amorphous negative electrode active material, a composite negative electrode active material, a battery negative electrode material and a battery.
背景技术Background technique
由于锂离子电池具有高的能量密度，高的工作电压和良好的循环稳定性，已被广泛应用于各种消费类电子产品、电动工具、电动汽车以及储能等领域。然而，当前商用锂离子电池负极大多采用石墨作为负极活性材料，理论容量有限(372mAh/g)，难以满足高能量密度、长续航时间的性能要求。因此，开发具有高容量的新型负极材料成为锂离子电池的重要研究方向。合金化负极具有高的理论容量，如硅的理论容量高达4200mAh/g，锡的理论容量高达994mAh/g，铝的理论容量高达2234mAh/g，作为高容量负极材料就有良好的应用前景。然而，合金类负极材料在合金化反应过程产生大的各向异性体积变化，导致开裂粉化，严重影响了电池的循环稳定性。非晶材料一方面具有各向同性的体积变化特性，可显著降低应力集中，同时微观结构较为疏松，可缓解体积膨胀。因此，非晶化处理是提升合金化类负极材料的结构稳定性有效手段之一。如，有现有技术记载一种负极活性物质用复合金属的合金方法，由Si、Ni以及过渡金属构成的合金，由Si xNi yM z(M为过渡金属，x、y、z分别为原子％)构成，以使上述x、y、z为50≤x≤90、1≤y≤49、1≤z≤49、以及x+y+z＝100的方式将复合金属进行合金化，使得在合金内的基体(Matrix)上存在非晶区域，或存在微细结晶区域和非晶区域。再如，现有技术还记载了一种含硅多孔非晶合金锂离子电池负极材料及其制备方法，该负极材料主要含有Si、Fe、B和其他元素，Si含量为10～60at％，B含量为10～35at％，Fe含量为0～55at％，其他元素含量为余量；其制备方法是将含Si的Fe基非晶合金或非晶纳米晶复合材料加入到稀盐酸中腐蚀除去Fe；然后，经静置、抽滤，洗涤，干燥，超声粉碎、过筛，得到含硅多孔非晶合金材料。这类硅基非晶材料对于提升其结构稳定性具有较好效果，然而硅本身是一种电子不良导体，导电性能差，电池电荷传输效率低，倍率性能低；另外，硅基非晶在合金化反应过程中体积膨胀依然很大(～300％)，极片需预留足够的缓冲空间，导致低的体积能量密度，或造成极片开裂失效。 Due to its high energy density, high operating voltage and good cycle stability, lithium-ion batteries have been widely used in various consumer electronics products, power tools, electric vehicles, and energy storage. However, most of the current commercial lithium-ion battery anodes use graphite as the anode active material, and the theoretical capacity is limited (372mAh/g), which makes it difficult to meet the performance requirements of high energy density and long battery life. Therefore, the development of new anode materials with high capacity has become an important research direction for lithium-ion batteries. Alloyed negative electrode has high theoretical capacity, such as silicon has a theoretical capacity of up to 4200mAh/g, tin has a theoretical capacity of up to 994mAh/g, and aluminum has a theoretical capacity of up to 2234mAh/g. It has a good application prospect as a high-capacity negative electrode material. However, alloy-based anode materials produce large anisotropic volume changes during the alloying reaction process, resulting in cracking and pulverization, which seriously affects the cycle stability of the battery. On the one hand, amorphous materials have isotropic volume change characteristics, which can significantly reduce stress concentration, and at the same time, the microstructure is relatively loose, which can alleviate volume expansion. Therefore, amorphization treatment is one of the effective means to improve the structural stability of alloyed anode materials. For example, there is prior art to record a kind of alloy method of composite metal for negative electrode active material, the alloy composed of Si, Ni and transition metal is composed of Six Ni y M z (M is transition metal, x, y, z are respectively Atomic %) composition, so that the above-mentioned x, y, z is 50 ≤ x ≤ 90, 1 ≤ y ≤ 49, 1 ≤ z ≤ 49, and x + y + z = 100, the composite metal is alloyed, so that There are amorphous regions on the matrix (Matrix) in the alloy, or there are fine crystal regions and amorphous regions. For another example, the prior art also records a silicon-containing porous amorphous alloy lithium-ion battery negative electrode material and its preparation method. The negative electrode material mainly contains Si, Fe, B and other elements, and the Si content is 10-60 at%. The content is 10-35at%, the content of Fe is 0-55at%, and the content of other elements is the balance; its preparation method is to add Si-containing Fe-based amorphous alloy or amorphous nanocrystalline composite material to dilute hydrochloric acid to corrode and remove Fe and then, standing still, suction filtering, washing, drying, ultrasonic pulverization and sieving to obtain a silicon-containing porous amorphous alloy material. This type of silicon-based amorphous material has a good effect on improving its structural stability. However, silicon itself is a poor conductor of electrons, with poor electrical conductivity, low battery charge transfer efficiency, and low rate capability; During the chemical reaction process, the volume expansion is still very large (~300%), and the pole piece needs to reserve enough buffer space, resulting in low volume energy density, or causing the pole piece to crack and fail.
发明内容Contents of the invention
本发明的目的在于提供一种铝基非晶负极活性材料、复合负极活性材料、电池负极材料和电池，以解决传统石墨负极比容量低，合金类负极膨胀粉化严重、循环性能差的难题。The object of the present invention is to provide an aluminum-based amorphous negative electrode active material, composite negative electrode active material, battery negative electrode material and battery to solve the problems of low specific capacity of traditional graphite negative electrodes, severe expansion and pulverization of alloy negative electrodes, and poor cycle performance.
为实现上述目的，本发明提供如下技术方案：To achieve the above object, the present invention provides the following technical solutions:
本发明第一方面提供一种铝基非晶负极活性材料，包括铝元素和改性金属元素，所述改性金属元素包括稀土元素和/或过渡金属元素。The first aspect of the present invention provides an aluminum-based amorphous negative electrode active material, which includes aluminum elements and modified metal elements, and the modified metal elements include rare earth elements and/or transition metal elements.
进一步地，所述铝基非晶负极活性材料中，铝元素的含量为50％～90％，稀土元素含量为0％～10％，过渡金属元素含量为0～50％，其中稀土元素和过渡金属元素的含量之和大于0；Further, in the aluminum-based amorphous negative electrode active material, the content of aluminum elements is 50% to 90%, the content of rare earth elements is 0% to 10%, and the content of transition metal elements is 0% to 50%. The sum of the contents of metal elements is greater than 0;
优选地，过渡金属元素含量大于0，稀土元素含量大于0；Preferably, the content of transition metal elements is greater than 0, and the content of rare earth elements is greater than 0;
更优选地，铝元素的含量为80％～90％，过渡金属元素含量大于0且小于等于20％。More preferably, the content of the aluminum element is 80%-90%, and the content of the transition metal element is greater than 0 and less than or equal to 20%.
进一步地，所述稀土元素包括钇、镝、镱中的一种或多种，过渡金属元素包括钛、铁、镍中的一种或多种。Further, the rare earth elements include one or more of yttrium, dysprosium, and ytterbium, and the transition metal elements include one or more of titanium, iron, and nickel.
进一步地，所述铝基非晶负极活性材料的制备方法包括机械球磨法、气相沉积法或快速冷却法。Further, the preparation method of the aluminum-based amorphous negative electrode active material includes a mechanical ball milling method, a vapor deposition method or a rapid cooling method.
本发明第二方面提供一种复合负极活性材料，所述复合负极活性材料由本发明第一方面提供的铝基非晶负极活性材料复合得到，包括石墨类材料和所述铝基非晶负极活性材料。The second aspect of the present invention provides a composite negative electrode active material, the composite negative electrode active material is obtained by compounding the aluminum-based amorphous negative electrode active material provided by the first aspect of the present invention, including graphite materials and the aluminum-based amorphous negative electrode active material .
进一步地，所述石墨类材料包括天然石墨、人造石墨、三维石墨海绵、中间相碳微球(MCMB)、软碳、硬碳、热解碳、石油焦、焦炭、石墨烯。Further, the graphite-based materials include natural graphite, artificial graphite, three-dimensional graphite sponge, mesocarbon microspheres (MCMB), soft carbon, hard carbon, pyrolytic carbon, petroleum coke, coke, and graphene.
进一步地，通过机械混合法、气相沉积法或水热合成法复合石墨类材料和铝基非晶负极活性材料。Further, the graphite-based material and the aluminum-based amorphous negative electrode active material are composited by a mechanical mixing method, a vapor deposition method or a hydrothermal synthesis method.
本发明第三方面提供一种电池负极材料，包括负极活性物质、导电剂和粘结剂，所述负极活性物质为本发明第一方面提供的铝基非晶负极活性材料或本发明第二方面提供的复合负极活性材料。The third aspect of the present invention provides a battery negative electrode material, including a negative electrode active material, a conductive agent and a binder, and the negative electrode active material is the aluminum-based amorphous negative electrode active material provided by the first aspect of the present invention or the second aspect of the present invention Provided composite negative electrode active materials.
本发明第四方面提供一种电池负极，包括集流体和本发明第三方面提供的电池负极材料。The fourth aspect of the present invention provides a battery negative electrode, including a current collector and the battery negative electrode material provided by the third aspect of the present invention.
本发明第五方面提供一种电池，包括本发明第四方面提供的电池负极。The fifth aspect of the present invention provides a battery, including the negative electrode of the battery provided by the fourth aspect of the present invention.
进一步地，本发明第五方面提供的电池为半电池如纽扣电池、全电池如锂离子电池、超级电容器、混合超级电容器等储能器件。Further, the battery provided by the fifth aspect of the present invention is an energy storage device such as a half battery such as a button battery, a full battery such as a lithium ion battery, a supercapacitor, or a hybrid supercapacitor.
与现有技术相比，本发明的有益效果是：本发明提供的铝基非晶负极活性材料、复合负极活性材料一方面体积变化小，且具有各向同性的体积变化特性，可有效抑制应力集中，另外较为疏松的微观 结构可有效缓解体积膨胀，从而显著提升结构稳定性；其中复合石墨类材料的复合负极活性材料比铝基非晶负极活性材料更能有效缓解体积膨胀；另一方面，铝基材料具有良好的导电性，可有效提升电荷传输效率，改善倍率性能。Compared with the prior art, the beneficial effects of the present invention are: the aluminum-based amorphous negative electrode active material and the composite negative electrode active material provided by the present invention have small volume change on the one hand, and have isotropic volume change characteristics, which can effectively suppress stress In addition, the relatively loose microstructure can effectively alleviate the volume expansion, thereby significantly improving the structural stability; among them, the composite negative electrode active material of the composite graphite material can effectively alleviate the volume expansion than the aluminum-based amorphous negative electrode active material; on the other hand, Aluminum-based materials have good electrical conductivity, which can effectively improve the charge transport efficiency and improve the rate performance.
附图说明Description of drawings
图1为实施例1制备的Al 83Ti 10Y 7非晶样品选区电子衍射图； Fig. 1 is the selected area electron diffraction pattern of the Al 83 Ti 10 Y 7 amorphous sample prepared in Example 1;
图2为实施例3制备的铝基非晶复合负极半电池循环性能图；Fig. 2 is the cycle performance diagram of the aluminum-based amorphous composite negative electrode half-cell prepared in Example 3;
图3为实施例106制备的铝基非晶复合负极所组合锂离子全电池的循环性能图。Fig. 3 is a cycle performance diagram of a lithium-ion full battery combined with an aluminum-based amorphous composite negative electrode prepared in Example 106.
具体实施方式Detailed ways
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.
本发明负极材料中所述的导电剂无任何限定，可举出乙炔黑、导电炭黑、石墨等本领域常用导电助剂，用于提高电极中产生的电子的传导性，使电池性能提高。The conductive agent described in the negative electrode material of the present invention is not limited in any way, and commonly used conductive additives in the field such as acetylene black, conductive carbon black, and graphite are used to improve the conductivity of electrons generated in the electrode and improve battery performance.
本发明负极材料中所述的粘结剂无任何限定，可举出丁苯橡胶(SBR)乳液、羧甲基纤维素(CMC)、聚环氧乙烷(PEO)、聚环氧丙烷(PPO)、聚偏氟乙烯(PVDF)、聚偏氟乙烯-六氟丙烯共聚物(PVDF-HFP)、聚丙烯腈(PAN)、聚丙烯酸甲酯(PMA)、聚甲基丙烯酸甲酯(PMMA)等示例。其中，通常使用PVDF。The binder described in the negative electrode material of the present invention is without any limitation, can enumerate styrene-butadiene rubber (SBR) emulsion, carboxymethyl cellulose (CMC), polyethylene oxide (PEO), polypropylene oxide (PPO) ), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polyacrylonitrile (PAN), polymethyl acrylate (PMA), polymethyl methacrylate (PMMA) and other examples. Among them, PVDF is generally used.
本发明负极中所述的集流体为非活性导电集流体，无任何限定，可举出铜箔(网)、钛箔(网)、铁箔(网)、镍箔(网)、碳布、导电尼龙等的示例，但不仅限于以上材料。The current collector described in the negative electrode of the present invention is an inactive conductive current collector, without any limitation, copper foil (net), titanium foil (net), iron foil (net), nickel foil (net), carbon cloth, Examples of conductive nylon and the like, but not limited to the above materials.
本发明组装电池中电解液并无限制，电解质盐可举出LiPF 6、LiBF 4、LiFSI、LiTFSI等示例，溶剂为酯类、砜类、醚类、腈类、烯烃类中的一种或几种，优选溶剂为碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸丙烯酯(PC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)等单一溶剂或组合溶剂。 The electrolyte solution in the assembled battery of the present invention is not limited, the electrolyte salt can be exemplified by LiPF 6 , LiBF 4 , LiFSI, LiTFSI, etc., and the solvent is one or more of esters, sulfones, ethers, nitriles, and olefins. A preferred solvent is a single solvent or a combination of solvents such as ethylene carbonate (EC), ethyl methyl carbonate (EMC), propylene carbonate (PC), dimethyl carbonate (DMC), and diethyl carbonate (DEC).
本发明组装电池中所采用的隔膜无限制，为本领域常规使用的绝缘的多孔聚合物薄膜或无机多孔薄膜等，如多孔聚丙烯薄膜、多孔聚乙烯薄膜、多孔复合聚合物薄膜、绝缘纤维纸或多孔陶瓷隔膜等，优选的采用绝缘纤维隔膜，如玻璃纤维隔膜等。The separator used in the assembled battery of the present invention is not limited, and is an insulating porous polymer film or an inorganic porous film etc. conventionally used in the art, such as porous polypropylene film, porous polyethylene film, porous composite polymer film, insulating fiber paper Or a porous ceramic diaphragm, preferably an insulating fiber diaphragm, such as a glass fiber diaphragm.
本发明提供的负极可以用于半电池如纽扣电池、全电池如锂离子电池、超级电容器、混合超级电容器等储能器件，正极活性材料无任何限制，可以是锂离子电池常用正极活性材料，如磷酸铁锂、钴酸锂、三元正极333型(镍：钴：锰摩尔比为3：3：3)、三元正极532型(镍：钴：锰摩尔比为5：3：2)、三元正极811型(镍：钴：锰摩尔比为8：1：1)。The negative electrode provided by the present invention can be used for energy storage devices such as half batteries such as button batteries, full batteries such as lithium ion batteries, supercapacitors, and hybrid supercapacitors. Lithium iron phosphate, lithium cobalt oxide, ternary positive electrode 333 type (nickel: cobalt: manganese molar ratio is 3:3:3), ternary positive electrode 532 type (nickel: cobalt: manganese molar ratio is 5:3:2), Ternary cathode 811 type (nickel:cobalt:manganese molar ratio is 8:1:1).
实施例1：制备基于Al 83Ti 10Y 7的非晶负极活性材料 Example 1: Preparation of an amorphous negative electrode active material based on Al 83 Ti 10 Y 7
以Al、Ti、Y粉末为原料，质量配比为Al:Ti:Y＝83:10:7，利用机械球磨法制备：将Al粉、Ti粉、Y粉按83:10:7的质量比加入球墨罐中，进行球磨，得到非晶Al 83Ti 10Y 7粉末，即为基于Al 83Ti 10Y 7的非晶负极活性材料。图1为制备的Al 83Ti 10Y 7非晶样品选区电子衍射图，从图1可以看出，Al 83Ti 10Y 7粉末是非晶结构。 Using Al, Ti, and Y powders as raw materials, the mass ratio is Al:Ti:Y=83:10:7, and it is prepared by mechanical ball milling: Al powder, Ti powder, and Y powder are mixed in a mass ratio of 83:10:7 Add it into a spherical ink tank and perform ball milling to obtain amorphous Al 83 Ti 10 Y 7 powder, which is the amorphous negative electrode active material based on Al 83 Ti 10 Y 7 . Figure 1 is the selected area electron diffraction pattern of the prepared Al 83 Ti 10 Y 7 amorphous sample. It can be seen from Figure 1 that the Al 83 Ti 10 Y 7 powder has an amorphous structure.
以制备的非晶Al 83Ti 10Y 7粉末作为负极活性物质制备负极、组装电池： Prepare the negative electrode and assemble the battery with the prepared amorphous Al 83 Ti 10 Y 7 powder as the negative electrode active material:
制备负极：选用铜箔作为非活性导电集流体，选用玻璃纤维作为隔膜，制备负极：(1)以铜箔为基地材料，使用无水乙醇对其表面清洁干净备用；(2)将制备的非晶Al 83Ti 10Y 7粉末作为负极活性物质，导电炭黑作为导电剂、粘结剂CMC按照质量比8:1:1均匀混合，然后加入N-甲基吡咯烷酮(NMP)溶剂进行充分搅拌获得浆料，将所述浆料均匀涂覆在步骤(1)得到的洁净铜箔表面，然后放入真空烘箱中进行干燥处理，烘烤温度为80℃，时间为24h，得到负极极片。 Prepare the negative electrode: select copper foil as the inactive conductive current collector, select glass fiber as the diaphragm, and prepare the negative electrode: (1) use copper foil as the base material, and use absolute ethanol to clean its surface for later use; (2) prepare the non- Crystalline Al 83 Ti 10 Y 7 powder is used as the negative electrode active material, conductive carbon black is used as the conductive agent, and the binder CMC is uniformly mixed according to the mass ratio of 8:1:1, and then N-methylpyrrolidone (NMP) solvent is added for thorough stirring to obtain Slurry, the slurry is uniformly coated on the surface of the clean copper foil obtained in step (1), and then placed in a vacuum oven for drying treatment at a temperature of 80° C. for 24 hours to obtain a negative electrode sheet.
组装电池：将LiPF 6电解质盐加入到EC和DEC(体积比1:1)混合溶剂中，然后充分搅拌溶解，得到电解液；在充满Ar的手套箱中，且H 2O与O 2含量均<0.1ppm条件下，将负极极片、玻璃纤维隔膜、对电极锂箔依次堆叠，加注电解液组装成扣式电池进行半电池性能测试，测试结果如表1所示。 Assemble the battery: add LiPF 6 electrolyte salt to the mixed solvent of EC and DEC (volume ratio 1:1), then fully stir and dissolve to obtain the electrolyte; in a glove box filled with Ar, and the content of H 2 O and O 2 Under the condition of <0.1ppm, the negative pole piece, the glass fiber separator, and the lithium foil of the counter electrode were stacked in sequence, and the electrolyte solution was added to assemble a coin cell for a half-cell performance test. The test results are shown in Table 1.
实施例2：制备基于Al 83Ti 10Y 7的非晶负极活性材料 Example 2: Preparation of an amorphous negative electrode active material based on Al 83 Ti 10 Y 7
与实施例1的区别仅在于：采用气相沉积直接在集流体表面沉积铝基非晶负极活性材料，具体操作为：使用Al、Ti和Y的复合溅射靶材，在铜箔表面沉积铝基非晶负极活性材料，得到负极极片。The only difference from Example 1 is that vapor deposition is used to directly deposit aluminum-based amorphous negative electrode active materials on the surface of the current collector. The specific operation is: use a composite sputtering target of Al, Ti and Y to deposit aluminum-based An amorphous negative electrode active material is obtained to obtain a negative electrode sheet.
按照与实施例1相同的方法组装纽扣电池进行半电池性能测试，测试结果如表1所示。The button battery was assembled according to the same method as in Example 1 to perform a half-cell performance test, and the test results are shown in Table 1.
实施例3：制备基于Al 83Ti 10Y 7的复合负极活性材料 Example 3: Preparation of a composite negative electrode active material based on Al 83 Ti 10 Y 7
(1)以铜箔为非活性导电集流体，使用无水乙醇对其表面清洁干净备用；(1) Use copper foil as an inactive conductive current collector, and use absolute ethanol to clean its surface for later use;
(2)以Al、Ti、Y粉末为原料，质量配比为Al:Ti:Y＝83:10:7，利用机械球磨法制备：将Al粉、 Ti粉、Y粉按83:10:7的质量比加入球墨罐中，进行球磨，得到非晶Al 83Ti 10Y 7粉末；将制备的非晶Al 83Ti 10Y 7粉末作为活性物质，导电炭黑作为导电剂、粘结剂CMC按照质量比8:1:1均匀混合，然后加入N-甲基吡咯烷酮(NMP)溶剂进行充分搅拌获得浆料，将所述浆料均匀涂覆在步骤(1)得到的洁净铜箔表面，得到铝基非晶/铜箔复合材料。 (2) Using Al, Ti, and Y powders as raw materials, the mass ratio is Al:Ti:Y=83:10:7, prepared by mechanical ball milling method: Al powder, Ti powder, and Y powder are mixed according to the ratio of 83:10:7 The mass ratio is added to the ball ink tank, and ball milling is carried out to obtain amorphous Al 83 Ti 10 Y 7 powder; the prepared amorphous Al 83 Ti 10 Y 7 powder is used as an active material, conductive carbon black is used as a conductive agent, and the binder CMC according to Mix evenly with a mass ratio of 8:1:1, then add N-methylpyrrolidone (NMP) solvent to fully stir to obtain a slurry, and uniformly coat the slurry on the surface of the clean copper foil obtained in step (1) to obtain an aluminum based amorphous/copper foil composites.
(3)在天然石墨中加入导电剂和粘结剂，质量比为天然石墨：导电剂：粘结剂＝8:1:1，其中导电剂为导电炭黑、粘结剂为CMC，然后加入N-甲基吡咯烷酮(NMP)溶剂进行充分搅拌获得浆料；将所述浆料均匀涂覆在步骤(2)得到的铝基非晶/铜箔复合材料表面，得到石墨/铝基非晶/铜箔复合材料，即为包覆到铜箔表面的复合负极活性材料。(3) Add conducting agent and binding agent in natural graphite, mass ratio is natural graphite: conducting agent: binding agent=8:1:1, wherein conducting agent is conductive carbon black, binding agent is CMC, then adds The N-methylpyrrolidone (NMP) solvent is fully stirred to obtain a slurry; the slurry is evenly coated on the surface of the aluminum-based amorphous/copper foil composite material obtained in step (2) to obtain graphite/aluminum-based amorphous/ The copper foil composite material is the composite negative electrode active material coated on the surface of the copper foil.
制备负极：将上述制备的石墨/铝基非晶/铜箔复合材料放入真空烘箱中进行干燥处理，烘烤温度为80℃，时间为24h，得到负极极片。Preparation of negative electrode: Put the graphite/aluminum-based amorphous/copper foil composite material prepared above into a vacuum oven for drying treatment at a temperature of 80° C. for 24 hours to obtain a negative electrode sheet.
组装电池：将LiPF 6电解质盐加入到EC和DEC(体积比1:1)混合溶剂中，然后充分搅拌溶解，得到电解液；在充满Ar的手套箱中，且H 2O与O 2含量均<0.1ppm条件下，将负极极片、玻璃纤维隔膜、对电极锂箔依次堆叠，加注电解液组装成扣式电池进行半电池性能测试，循环性能图如图2所示。 Assemble the battery: add LiPF 6 electrolyte salt to the mixed solvent of EC and DEC (volume ratio 1:1), then fully stir and dissolve to obtain the electrolyte; in a glove box filled with Ar, and the content of H 2 O and O 2 Under the condition of <0.1ppm, the negative electrode sheet, the glass fiber separator, and the lithium foil of the counter electrode were stacked in sequence, and the electrolyte was filled to assemble a button cell for half-cell performance testing. The cycle performance diagram is shown in Figure 2.
实施例4：制备基于Al 83Ti 10Y 7的复合负极活性材料 Example 4: Preparation of a composite negative electrode active material based on Al 83 Ti 10 Y 7
与实施例3的不同仅在于：调换步骤(2)和步骤(3)，即先得到石墨/铜箔复合材料，再将非晶Al 83Ti 10Y 7粉末、导电炭黑和粘结剂CMC按照相同配比混合制成的浆料均匀涂覆在石墨/铜箔复合材料表面。 The difference from Example 3 is only that step (2) and step (3) are exchanged, that is, graphite/copper foil composite material is obtained first, and then amorphous Al 83 Ti 10 Y 7 powder, conductive carbon black and binder CMC The slurry prepared by mixing according to the same proportion is evenly coated on the surface of the graphite/copper foil composite material.
按照与实施例3相同的方法制备负极、组装纽扣电池，并进行半电池性能测试，测试结果如表1所示。According to the same method as in Example 3, the negative electrode was prepared, the button cell was assembled, and the half-cell performance test was carried out. The test results are shown in Table 1.
实施例5-86：制备其它铝基非晶的复合负极活性材料Example 5-86: Preparation of other aluminum-based amorphous composite negative electrode active materials
实施例5-86与实施例3不同仅在于：采用不同的过渡金属元素和稀土元素，具体如下表1。负极的制备和纽扣电池的组装均与实施例3相同。The difference between Examples 5-86 and Example 3 is that different transition metal elements and rare earth elements are used, as shown in Table 1 below. The preparation of the negative electrode and the assembly of the button cell were the same as in Example 3.
对比例1Comparative example 1
以纯铝作为负极活性物质，按照与实施例1相同的方法制备负极、组装电池。Using pure aluminum as the negative electrode active material, the same method as in Example 1 was used to prepare the negative electrode and assemble the battery.
对比例2Comparative example 2
以天然石墨为负极活性物质，按照与实施例1相同的方法制备负极、组装电池。Using natural graphite as the negative electrode active material, the same method as in Example 1 was used to prepare the negative electrode and assemble the battery.
将实施例1-86、对比例1、对比例2负极活性材料组装的电池进行半电池性能测试，得到如下表1：The batteries assembled with negative electrode active materials in Examples 1-86, Comparative Example 1, and Comparative Example 2 were tested for half-cell performance, and the following table 1 was obtained:
表1实施例1-86、对比例1、对比例2的负极活性材料和电池的电化学性能Table 1 Embodiment 1-86, comparative example 1, the negative electrode active material of comparative example 2 and the electrochemical performance of battery
Figure PCTCN2021138187-appb-000001
Figure PCTCN2021138187-appb-000001
Figure PCTCN2021138187-appb-000002
Figure PCTCN2021138187-appb-000002
Figure PCTCN2021138187-appb-000003
Figure PCTCN2021138187-appb-000003
Figure PCTCN2021138187-appb-000004
Figure PCTCN2021138187-appb-000004
从表1可以看出，稀土金属和过渡金属元素引入后电池的循环性能和容量保持率更高，这就说明本发明提供的技术方案对提高负极材料的电化学性能具有明显效果。It can be seen from Table 1 that the cycle performance and capacity retention rate of the battery after the introduction of rare earth metals and transition metal elements are higher, which shows that the technical solution provided by the present invention has a significant effect on improving the electrochemical performance of the negative electrode material.
实施例87Example 87
实施例87与实施例3不同仅在于：采用不同的非活性导电集流体。分别采用铜箔(网)、钛箔(网)、铁箔(网)、镍箔(网)、碳布、导电尼龙作为非活性导电集流体，采用与实施例3相同的 方法制备负极并组装纽扣电池。The only difference between Example 87 and Example 3 is that different inactive conductive current collectors are used. Copper foil (network), titanium foil (network), iron foil (network), nickel foil (network), carbon cloth, and conductive nylon were used as inactive conductive current collectors, and the negative electrode was prepared and assembled in the same way as in Example 3. Button Battery.
采用相同方法测试纽扣电池的电化学性能，电池的循环性能和容量保持率均与实施例3相近，这就说明本发明提供的技术方案适用各类集流体。Using the same method to test the electrochemical performance of the button battery, the cycle performance and capacity retention rate of the battery are similar to those of Example 3, which shows that the technical solution provided by the present invention is applicable to various current collectors.
实施例88-91Examples 88-91
实施例88-91与实施例3不同的是采用不同的隔膜材料。采用与实施例3相同的方法制备负极并组装纽扣电池，用相同方法测试纽扣电池的电化学性能，具体如下表2。The difference between Examples 88-91 and Example 3 is that different diaphragm materials are used. The same method as in Example 3 was used to prepare the negative electrode and assemble the button battery, and the electrochemical performance of the button battery was tested by the same method, as shown in Table 2 below.
表2实施例88-91与实施例3的隔膜种类、电池的电化学性能Table 2 Embodiment 88-91 and the separator type of embodiment 3, the electrochemical performance of battery
Figure PCTCN2021138187-appb-000005
Figure PCTCN2021138187-appb-000005
实施例92-97Examples 92-97
实施例92-97与实施例3不同的是采用不同的石墨类材料。采用与实施例3相同的方法制备负极并组装纽扣电池，用相同方法测试纽扣电池的电化学性能，具体如下表3。The difference between Embodiment 92-97 and Embodiment 3 is that different graphite materials are used. The same method as in Example 3 was used to prepare the negative electrode and assemble the button battery, and the electrochemical performance of the button battery was tested by the same method, as shown in Table 3 below.
表3实施例92-97与实施例3的石墨类材料、电池的电化学性能Table 3 Embodiment 92-97 and the graphite material of embodiment 3, the electrochemical performance of battery
Figure PCTCN2021138187-appb-000006
Figure PCTCN2021138187-appb-000006
Figure PCTCN2021138187-appb-000007
Figure PCTCN2021138187-appb-000007
从表3可以看出，天然石墨和人造石墨的循环圈数最长，这是因为在锂离子在***过程中，不会导致其结构的崩塌。It can be seen from Table 3 that the number of cycles of natural graphite and artificial graphite is the longest, because the lithium ion will not lead to the collapse of its structure during the insertion process.
实施例98Example 98
实施例98与实施例3不同的是：采用球磨法复合铝基非晶材料和石墨类材料。具体操作为：The difference between Example 98 and Example 3 is that the aluminum-based amorphous material and graphite-based material are compounded by ball milling. The specific operation is:
(1)以铜箔为非活性导电集流体，使用无水乙醇对其表面清洁干净备用；(1) Use copper foil as an inactive conductive current collector, and use absolute ethanol to clean its surface for later use;
(2)以Al、Ti、Y粉末为原料，质量配比为Al:Ti:Y＝83:10:7，利用机械球磨法制备：将Al粉、Ti粉、Y粉按83:10:7的质量比加入球墨罐中，进行球磨，得到非晶Al 83Ti 10Y 7粉末； (2) Using Al, Ti, and Y powders as raw materials, the mass ratio is Al:Ti:Y=83:10:7, prepared by mechanical ball milling: Al powder, Ti powder, and Y powder are mixed according to the ratio of 83:10:7 The mass ratio is added to the ball ink tank, and ball milled to obtain amorphous Al 83 Ti 10 Y 7 powder;
(3)在天然石墨中加入步骤(2)得到的非晶Al 83Ti 10Y 7粉末、导电剂导电炭黑、粘结剂CMC，其中质量比为(天然石墨和非晶Al 83Ti 10Y 7粉末之和)：导电剂：粘结剂＝8:1:1，然后加入N-甲基吡咯烷酮(NMP)溶剂进行充分搅拌获得浆料；即得到复合负极活性材料。 (3) Add the amorphous Al 83 Ti 10 Y 7 powder that step (2) obtains in natural graphite, conductive agent conductive carbon black, binding agent CMC, wherein mass ratio is (natural graphite and amorphous Al 83 Ti 10 Y The sum of 7 powders): conductive agent: binder = 8:1:1, and then add N-methylpyrrolidone (NMP) solvent for sufficient stirring to obtain a slurry; that is, a composite negative electrode active material is obtained.
(4)将步骤(3)浆料均匀涂覆在步骤(1)得到的铜箔表面，然后放入真空烘箱中进行干燥处理，烘烤温度为80℃，时间为24h，得到负极极片。(4) Evenly coat the slurry in step (3) on the surface of the copper foil obtained in step (1), and then put it into a vacuum oven for drying treatment at a temperature of 80° C. for 24 hours to obtain a negative electrode sheet.
采用与实施例3相同的方法组装纽扣电池，用相同方法测试纽扣电池的电化学性能，得到初始放电比容量为426mAh/g，可逆放电比容量为400mAh/g，循环圈数600，最后放电容量为362mAh/g，容量保持率为85％。Adopt the method identical with embodiment 3 to assemble button battery, test the electrochemical performance of button battery with the same method, obtain initial discharge specific capacity and be 426mAh/g, reversible discharge specific capacity is 400mAh/g, cycle number 600, final discharge capacity It was 362mAh/g, and the capacity retention rate was 85%.
实施例99Example 99
实施例99与实施例3不同的是：采用气相沉积法制备铝基非晶材料，然后与石墨类材料复合。具体操作为：The difference between Example 99 and Example 3 is that the aluminum-based amorphous material is prepared by vapor deposition, and then compounded with graphite-based materials. The specific operation is:
(1)以铜箔为非活性导电集流体，使用无水乙醇对其表面清洁干净备用；(1) Use copper foil as an inactive conductive current collector, and use absolute ethanol to clean its surface for later use;
(2)以Al、Ti复合和Y作为溅射靶材，采用气相沉积方法，在铜箔表面沉积一层铝基非晶活性材料，得到铝基非晶/导电集流体复合材料；(2) Using Al, Ti composite and Y as the sputtering target material, a layer of aluminum-based amorphous active material is deposited on the surface of copper foil by vapor deposition method to obtain aluminum-based amorphous/conductive current collector composite material;
(3)在天然石墨中加入导电剂和粘结剂，质量比为天然石墨：导电剂：粘结剂＝8:1:1，其中导电剂为导电炭黑、粘结剂为CMC，然后加入N-甲基吡咯烷酮(NMP)溶剂进行充分搅拌获得浆料，将所述浆料均匀涂覆在步骤(2)所获得的铝基非晶/导电集流体复合材料表面，得到石墨/铝基非晶/ 导电集流体复合材料。(3) Add conducting agent and binding agent in natural graphite, mass ratio is natural graphite: conducting agent: binding agent=8:1:1, wherein conducting agent is conductive carbon black, binding agent is CMC, then adds The N-methylpyrrolidone (NMP) solvent is fully stirred to obtain a slurry, and the slurry is uniformly coated on the surface of the aluminum-based amorphous/conductive current collector composite material obtained in step (2) to obtain a graphite/aluminum-based amorphous crystal/conductive current collector composites.
(4)将步骤(3)所获得的石墨/铝基非晶/导电集流体复合材料放入真空烘箱中进行干燥处理，烘烤温度为80℃，时间为24h，得到负极极片。(4) Put the graphite/aluminum-based amorphous/conductive current collector composite material obtained in step (3) into a vacuum oven for drying treatment at a temperature of 80° C. for 24 hours to obtain a negative electrode sheet.
采用与实施例3相同的方法组装纽扣电池，用相同方法测试纽扣电池的电化学性能，得到初始放电比容量为418mAh/g，可逆放电比容量为411mAh/g，循环圈数500，最后放电容量为301mAh/g，容量保持率72％。Adopt the method identical with embodiment 3 to assemble button battery, test the electrochemical performance of button battery with the same method, obtain initial discharge specific capacity and be 418mAh/g, reversible discharge specific capacity is 411mAh/g, cycle number 500, final discharge capacity It was 301mAh/g, and the capacity retention rate was 72%.
实施例100Example 100
实施例100与实施例99不同的是：采用不同的复合工艺复合铝基非晶材料和石墨类材料，具体操作为：The difference between Example 100 and Example 99 is that different composite processes are used to composite aluminum-based amorphous materials and graphite materials, and the specific operations are as follows:
(1)取人造石墨，放入烘箱中，烘烤温度为60℃，时间为24h。(1) Take artificial graphite and put it into an oven at a temperature of 60° C. for 24 hours.
(2)步骤(1)制备好的石墨类活性材料放入气相沉积的炉子中，以Al、Ti复合和Y作为溅射靶材，采用气相沉积方法，在石墨类活性材料颗粒表面沉积一层铝基非晶活性物质，得到具有铝基非晶包覆层的石墨类活性材料，即得到复合负极活性材料。(2) The graphite active material prepared in step (1) is put into a vapor deposition furnace, and Al, Ti composite and Y are used as sputtering targets, and a layer of graphite active material is deposited on the surface of the graphite active material particles by vapor deposition. The aluminum-based amorphous active material is used to obtain a graphite-based active material with an aluminum-based amorphous coating layer, that is, a composite negative electrode active material is obtained.
制备负极：以铜箔为非活性导电集流体，使用无水乙醇对其表面清洁干净备用；在制备得到的复合负极活性材料中加入导电剂和粘结剂，质量比复合负极活性材料：导电剂：粘结剂＝8:1:1，其中导电剂为导电炭黑、粘结剂为CMC，然后加入N-甲基吡咯烷酮(NMP)溶剂进行充分搅拌获得浆料，将所述浆料均匀涂覆在洁净的铜箔表面，然后经真空烘箱中进行干燥处理，烘烤温度为80℃，时间为24h，得到负极极片。Preparation of negative electrode: use copper foil as an inactive conductive current collector, use absolute ethanol to clean its surface for later use; add conductive agent and binder to the prepared composite negative electrode active material, and the mass ratio of composite negative electrode active material: conductive agent : binding agent=8:1:1, wherein the conductive agent is conductive carbon black, the binding agent is CMC, then add N-methylpyrrolidone (NMP) solvent and carry out sufficient stirring to obtain slurry, and the slurry is evenly coated Cover the surface of clean copper foil, and then carry out drying treatment in a vacuum oven at a baking temperature of 80° C. for 24 hours to obtain a negative electrode sheet.
组装电池：将LiPF 6电解质盐加入到EC和DEC(体积比1:1)混合溶剂中，然后充分搅拌溶解，得到电解液；在充满Ar的手套箱中，且H 2O与O 2含量均<0.1ppm条件下，将负极极片、玻璃纤维隔膜、对电极锂箔依次堆叠，加注电解液组装成扣式电池进行半电池性能测试，得到初始放电比容量为435mAh/g，可逆放电比容量为421mAh/g，循环圈数600，最后放电容量为352mAh/g，容量保持率81％。 Assemble the battery: add LiPF 6 electrolyte salt to the mixed solvent of EC and DEC (volume ratio 1:1), then fully stir and dissolve to obtain the electrolyte; in a glove box filled with Ar, and the content of H 2 O and O 2 Under the condition of <0.1ppm, the negative electrode sheet, the glass fiber separator, and the lithium foil of the counter electrode were stacked in sequence, and the electrolyte was filled to assemble a button battery for half-cell performance testing. The initial discharge specific capacity was 435mAh/g, and the reversible discharge ratio The capacity is 421mAh/g, the number of cycles is 600, the final discharge capacity is 352mAh/g, and the capacity retention rate is 81%.
实施例101Example 101
采用本发明实施例3制备的铝基非晶复合负极构筑锂离子全电池，其中正极活性材料采用磷酸铁锂，隔膜优选玻璃纤维隔膜，电解液采用1M LiPF 6/EC:DEC＝1:1，组装成扣式电池。具体制备步骤如下： The aluminum-based amorphous composite negative electrode prepared in Example 3 of the present invention is used to construct a lithium-ion full battery, wherein the positive electrode active material is lithium iron phosphate, the separator is preferably a glass fiber separator, and the electrolyte is 1M LiPF 6 /EC:DEC=1:1, Assemble into a button cell. Concrete preparation steps are as follows:
(1)负极的制备同实施例3；(1) the preparation of negative pole is with embodiment 3;
(2)制备正极：将磷酸铁锂作为正极活性材料与导电炭黑和聚偏氟乙烯(PVDF)按照8:1:1的质量配比混合均匀，加入N-甲基吡咯烷酮(NMP)溶剂进行充分搅拌获得浆料，然后将所述浆料均匀涂覆在涂碳铝箔表面，之后放入真空烘箱进行干燥处理，烘烤温度为80℃，烘烤时间为24h。(2) Prepare the positive electrode: mix lithium iron phosphate as the positive electrode active material with conductive carbon black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, add N-methylpyrrolidone (NMP) solvent to carry out Stir well to obtain a slurry, and then evenly coat the slurry on the surface of the carbon-coated aluminum foil, and then put it into a vacuum oven for drying treatment, the baking temperature is 80° C., and the baking time is 24 hours.
将LiPF 6电解质盐加入到EC和DEC(体积比1:1)混合溶剂中，然后充分搅拌溶解，得到电解液；在充满Ar的手套箱中，且H 2O与O 2含量均<0.1ppm条件下，将负极极片、玻璃纤维隔膜、正极极片依次堆叠，加注电解液组装成扣式电池进行半电池性能测试。 Add LiPF 6 electrolyte salt to the mixed solvent of EC and DEC (volume ratio 1:1), then fully stir and dissolve to obtain the electrolyte solution; in a glove box filled with Ar, and the content of H 2 O and O 2 are both <0.1ppm Under the same conditions, the negative pole piece, the glass fiber separator, and the positive pole piece were stacked in sequence, filled with electrolyte and assembled into a button battery for half-cell performance testing.
实施例102-105Examples 102-105
实施例102-105与实施例101的不同仅在于：正极活性材料不同。The only difference between Examples 102-105 and Example 101 is that the positive electrode active material is different.
实施例102-105的正极活性材料和组装得到的锂离子全电池的电化学性能如下表4所示：The electrochemical properties of the positive electrode active materials of Examples 102-105 and the assembled lithium-ion full battery are shown in Table 4 below:
表4.本发明实施例102-105的全电池测试数据Table 4. Full battery test data of Examples 102-105 of the present invention
Figure PCTCN2021138187-appb-000008
Figure PCTCN2021138187-appb-000008
实施例106Example 106
采用本发明实施例3制备的铝基非晶复合负极构筑锂离子全电池，其中正极活性材料采用膨胀石墨，隔膜优选玻璃纤维隔膜，电解液采用4M LiPF 6/EMC+2％VC，组装成扣式电池。具体制备步骤如下： The aluminum-based amorphous composite negative electrode prepared in Example 3 of the present invention is used to construct a lithium-ion full battery, wherein the positive electrode active material is expanded graphite, the separator is preferably a glass fiber separator, and the electrolyte is 4M LiPF 6 /EMC+2% VC, assembled into a button battery. Concrete preparation steps are as follows:
(1)负极的制备同实施例3；(1) the preparation of negative pole is with embodiment 3;
(2)制备正极：将膨胀石墨作为正极活性材料，与导电炭黑和聚偏氟乙烯(PVDF)按照8:1:1的质量配比混合均匀，加入N-甲基吡咯烷酮(NMP)溶剂进行充分搅拌获得浆料，然后将所述浆料均匀涂覆在涂碳铝箔表面，之后放入真空烘箱进行干燥处理，烘烤温度为80℃，烘烤时间为24h。(2) Prepare the positive electrode: use expanded graphite as the positive electrode active material, mix it with conductive carbon black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, add N-methylpyrrolidone (NMP) solvent for Stir well to obtain a slurry, and then evenly coat the slurry on the surface of the carbon-coated aluminum foil, and then put it into a vacuum oven for drying treatment, the baking temperature is 80° C., and the baking time is 24 hours.
将LiPF 6电解质盐加入到EC和DEC(体积比1:1)混合溶剂中，然后充分搅拌溶解，得到电解液；在充满Ar的手套箱中，且H 2O与O 2含量均<0.1ppm条件下，将负极极片、玻璃纤维隔膜、正极极片依次堆叠，加注电解液组装成扣式电池，进行电化学性能测试，循环性能图如图3所示，初始放电容量为102mAh/g，可逆放电容量为100mAh/g，循环圈数900，最后放电容量为93mAh/g，容量保持率为91％。 Add LiPF 6 electrolyte salt to the mixed solvent of EC and DEC (volume ratio 1:1), then fully stir and dissolve to obtain the electrolyte solution; in a glove box filled with Ar, and the content of H 2 O and O 2 are both <0.1ppm Under the same conditions, the negative pole piece, the glass fiber separator, and the positive pole piece were stacked in sequence, and the electrolyte was filled to assemble a button battery, and the electrochemical performance test was carried out. The cycle performance diagram is shown in Figure 3, and the initial discharge capacity is 102mAh/g , the reversible discharge capacity is 100mAh/g, the number of cycles is 900, the final discharge capacity is 93mAh/g, and the capacity retention rate is 91%.
实施例107-110Examples 107-110
实施例107-110与实施例101的不同在于：电解液不同。The difference between Examples 107-110 and Example 101 is that the electrolyte solution is different.
实施例101、107-110的电解液中的盐和溶剂、以及组装得到的锂离子全电池的电化学性能如下表5所示：The salts and solvents in the electrolytes of Examples 101, 107-110, and the electrochemical properties of the assembled lithium-ion full battery are shown in Table 5 below:
表5实施例101、107-110的电解液中的盐和溶剂、以及组装得到的锂离子全电池的电化学性能Salt and solvent in the electrolyte of table 5 embodiment 101,107-110, and the electrochemical performance of the lithium-ion full battery that assembles
Figure PCTCN2021138187-appb-000009
Figure PCTCN2021138187-appb-000009
以上仅为本发明的优选实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。The above are only preferred embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process conversion made by using the description of the present invention and the contents of the accompanying drawings, or directly or indirectly used in other related technical fields , are all included in the scope of patent protection of the present invention in the same way.

Claims (10)

  1. 一种铝基非晶负极活性材料，其特征在于，包括铝元素和改性金属元素，所述改性金属元素包括稀土元素和/或过渡金属元素。An aluminum-based amorphous negative electrode active material is characterized in that it includes aluminum elements and modified metal elements, and the modified metal elements include rare earth elements and/or transition metal elements.
  2. 根据权利要求1所述的铝基非晶负极活性材料，其特征在于，所述铝基非晶负极活性材料中，铝元素的含量为50％～90％，稀土元素含量为0％～10％，过渡金属元素含量为0～50％，其中稀土元素和过渡金属元素的含量之和大于0；The aluminum-based amorphous negative electrode active material according to claim 1, characterized in that, in the aluminum-based amorphous negative electrode active material, the content of the aluminum element is 50% to 90%, and the content of the rare earth element is 0% to 10%. , the content of transition metal elements is 0% to 50%, wherein the sum of the contents of rare earth elements and transition metal elements is greater than 0;
    优选地，过渡金属元素含量大于0，稀土元素含量大于0；Preferably, the content of transition metal elements is greater than 0, and the content of rare earth elements is greater than 0;
    更优选地，铝元素的含量为80％～90％，过渡金属元素含量大于0且小于等于20％。More preferably, the content of the aluminum element is 80%-90%, and the content of the transition metal element is greater than 0 and less than or equal to 20%.
  3. 根据权利要求1所述的铝基非晶负极活性材料，其特征在于，所述稀土元素包括钇、镝、镱中的一种或多种，过渡金属元素包括钛、铁、镍中的一种或多种。The aluminum-based amorphous negative electrode active material according to claim 1, wherein the rare earth element includes one or more of yttrium, dysprosium, and ytterbium, and the transition metal element includes one of titanium, iron, and nickel. or more.
  4. 根据权利要求1所述的铝基非晶负极活性材料，其特征在于，所述铝基非晶负极活性材料的制备方法包括机械球磨法、气相沉积法或快速冷却法。The aluminum-based amorphous negative electrode active material according to claim 1, wherein the preparation method of the aluminum-based amorphous negative electrode active material comprises a mechanical ball milling method, a vapor phase deposition method or a rapid cooling method.
  5. 一种由权利要求1-4任一项所述铝基非晶负极活性材料复合得到的复合负极活性材料，其特征在于，包括石墨类材料和所述铝基非晶负极活性材料。A composite negative electrode active material obtained by compounding the aluminum-based amorphous negative electrode active material according to any one of claims 1-4, characterized in that it comprises a graphite material and the aluminum-based amorphous negative electrode active material.
  6. 根据权利要求5所述的复合负极活性材料，其特征在于，所述石墨类材料包括天然石墨、人造石墨、三维石墨海绵、中间相碳微球、软碳、硬碳、热解碳、石油焦、焦炭、石墨烯。The composite negative electrode active material according to claim 5, wherein said graphite materials include natural graphite, artificial graphite, three-dimensional graphite sponge, mesocarbon microspheres, soft carbon, hard carbon, pyrolytic carbon, petroleum coke , coke, graphene.
  7. 根据权利要求5所述的复合负极活性材料，其特征在于，通过机械混合法、气相沉积法或水热合成法复合石墨类材料和铝基非晶负极活性材料。The composite negative electrode active material according to claim 5, characterized in that the graphite material and the aluminum-based amorphous negative electrode active material are composited by mechanical mixing, vapor deposition or hydrothermal synthesis.
  8. 一种电池负极材料，其特征在于，包括负极活性物质、导电剂和粘结剂，所述负极活性物质为权利要求1-4任一项所述铝基非晶负极活性材料或权利要求5-7任一项所述复合负极活性材料。A battery negative electrode material, characterized in that it includes a negative electrode active material, a conductive agent and a binding agent, and the negative electrode active material is the aluminum-based amorphous negative electrode active material according to any one of claims 1-4 or claim 5- 7. The composite negative electrode active material described in any one.
  9. 一种电池负极，其特征在于，包括集流体和权利要求8所述的电池负极材料。A battery negative electrode, characterized in that it comprises a current collector and the battery negative electrode material according to claim 8.
  10. 一种电池，其特征在于，包括权利要求9所述的电池负极。A battery, characterized by comprising the negative electrode of the battery according to claim 9.
PCT/CN2021/138187 2021-12-15 2021-12-15 Aluminum-based amorphous negative electrode active material, composite negative electrode active material, battery negative electrode material, and battery WO2023108458A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2021/138187 WO2023108458A1 (en) 2021-12-15 2021-12-15 Aluminum-based amorphous negative electrode active material, composite negative electrode active material, battery negative electrode material, and battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2021/138187 WO2023108458A1 (en) 2021-12-15 2021-12-15 Aluminum-based amorphous negative electrode active material, composite negative electrode active material, battery negative electrode material, and battery

Publications (1)

Publication Number Publication Date
WO2023108458A1 true WO2023108458A1 (en) 2023-06-22

Family

ID=86775006

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/138187 WO2023108458A1 (en) 2021-12-15 2021-12-15 Aluminum-based amorphous negative electrode active material, composite negative electrode active material, battery negative electrode material, and battery

Country Status (1)

Country Link
WO (1) WO2023108458A1 (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04332472A (en) * 1991-05-07 1992-11-19 Matsushita Electric Ind Co Ltd Negative pole for nonaqueous electrolyte secondary battery
US20010031398A1 (en) * 2000-03-16 2001-10-18 Takuya Hashimoto Negative electrode for lithium secondary battery
CN1419303A (en) * 2001-09-28 2003-05-21 株式会社东芝 Negative electrode material for nonelectrolyte cell and making method, negative electrode and cell
US20080076017A1 (en) * 2005-03-31 2008-03-27 Hideharu Takezawa Lithium Secondary Battery
CN103996826A (en) * 2013-02-15 2014-08-20 三星Sdi株式会社 Negative active material, and negative electrode and lithium battery each including the negative active material
CN111816856A (en) * 2020-07-21 2020-10-23 深圳先进技术研究院 Composite material, preparation method thereof and negative electrode
CN113921802A (en) * 2021-09-30 2022-01-11 中国电子科技集团公司第十八研究所 Aluminum alloy negative electrode material for battery, alkaline electrolyte corrosion inhibitor, preparation method and application

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04332472A (en) * 1991-05-07 1992-11-19 Matsushita Electric Ind Co Ltd Negative pole for nonaqueous electrolyte secondary battery
US20010031398A1 (en) * 2000-03-16 2001-10-18 Takuya Hashimoto Negative electrode for lithium secondary battery
CN1419303A (en) * 2001-09-28 2003-05-21 株式会社东芝 Negative electrode material for nonelectrolyte cell and making method, negative electrode and cell
US20080076017A1 (en) * 2005-03-31 2008-03-27 Hideharu Takezawa Lithium Secondary Battery
CN103996826A (en) * 2013-02-15 2014-08-20 三星Sdi株式会社 Negative active material, and negative electrode and lithium battery each including the negative active material
CN111816856A (en) * 2020-07-21 2020-10-23 深圳先进技术研究院 Composite material, preparation method thereof and negative electrode
CN113921802A (en) * 2021-09-30 2022-01-11 中国电子科技集团公司第十八研究所 Aluminum alloy negative electrode material for battery, alkaline electrolyte corrosion inhibitor, preparation method and application

Similar Documents

Publication Publication Date Title
He et al. Preparation and electrochemical properties of Ag-modified TiO2 nanotube anode material for lithium–ion battery
WO2022267534A1 (en) Lithium metal negative electrode plate, electrochemical apparatus, and electronic device
WO2022016951A1 (en) Silicon-based negative electrode material, negative electrode, and lithium-ion battery and preparation method therefor
CN112151764A (en) Electrode plate and preparation method and application thereof
WO2022033065A1 (en) Negative electrode plate and secondary battery
TWI725822B (en) Lithium battery and anode material thereof
WO2014040410A1 (en) Lithium-rich solid solution positive electrode composite material and method for preparing same, lithium ion battery positive electrode plate and lithium ion battery
WO2022267550A1 (en) Positive electrode active material, electrochemical apparatus and electronic device
Deng et al. High-performance SiMn/C composite anodes with integrating inactive Mn4Si7 alloy for lithium-ion batteries
CN102709531A (en) Lithium ion battery and cathode thereof
Luo et al. In situ construction of efficient interface layer with lithiophilic nanoseeds toward dendrite‐free and low N/P ratio Li metal batteries
Natalia et al. Graphite/Li 2 ZrO 3 anode for a LiFePO 4 battery
CN115020682B (en) Preparation method of high-energy-density quick-charging graphite cathode material
WO2023108458A1 (en) Aluminum-based amorphous negative electrode active material, composite negative electrode active material, battery negative electrode material, and battery
CN113594456B (en) Positive electrode slurry, preparation method thereof, positive plate and lithium ion battery
Lu et al. Preparation, characterization and electrochemical performance of silicon coated natural graphite as anode for lithium ion batteries
CN112864374B (en) Lithium cathode with gradient distribution of lithium content, preparation method thereof and lithium secondary battery
CN114824192A (en) Composite positive electrode material, battery positive electrode, lithium battery and application of composite positive electrode material
CN113206213A (en) Silicon-based composite electrode and preparation method and application thereof
CN114420914A (en) Aluminum-based amorphous negative electrode active material, composite negative electrode active material, battery negative electrode material and battery
CN111646472A (en) Method for in-situ preparation of porous silicon-carbon composite negative electrode material
CN113921914B (en) Electrolyte solution, and electrochemical device and electronic device using same
CN113594452B (en) Negative plate, preparation method thereof and lithium ion battery
CN114824168B (en) Lithium supplementing agent for positive electrode of lithium ion battery, lithium supplementing method, positive electrode plate, lithium supplementing slurry and battery
CN114583137B (en) Method for modifying carbon surface by sulfur doped phosphorus and application thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21967598

Country of ref document: EP

Kind code of ref document: A1