CN117080397A - Negative electrode composite material for high-power energy storage battery, and preparation method and application thereof - Google Patents

Negative electrode composite material for high-power energy storage battery, and preparation method and application thereof Download PDF

Info

Publication number
CN117080397A
CN117080397A CN202311101869.0A CN202311101869A CN117080397A CN 117080397 A CN117080397 A CN 117080397A CN 202311101869 A CN202311101869 A CN 202311101869A CN 117080397 A CN117080397 A CN 117080397A
Authority
CN
China
Prior art keywords
negative electrode
composite material
electrode composite
solution
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202311101869.0A
Other languages
Chinese (zh)
Inventor
焦坤
郑军欣
黄洪涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huizhou Heteng Energy Technology Co ltd
Original Assignee
Huizhou Heteng Energy Technology Co ltd
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 Huizhou Heteng Energy Technology Co ltd filed Critical Huizhou Heteng Energy Technology Co ltd
Priority to CN202311101869.0A priority Critical patent/CN117080397A/en
Publication of CN117080397A publication Critical patent/CN117080397A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • 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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

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

Abstract

The invention provides a negative electrode composite material for a high-power energy storage battery, and a preparation method and application thereof, wherein the preparation method comprises the following steps: graphitizing and crushing oxidized anthracite at low temperature, adding the pulverized anthracite into a metal chloride solution, carrying out hydrothermal reaction with an alkaline solution and an aluminum-based coupling agent, and drying filter residues to obtain a graphite precursor intermediate material; adding cerium acetate, cobalt chloride and ethylenediamine into an alcohol solvent to obtain a coating solution; adding the graphite precursor intermediate material into the coating liquid, spray-drying, and carbonizing to obtain a bimetal/amorphous carbon coated coal-based composite material; after being applied to a lithium ion battery, the negative electrode composite material has the characteristics of excellent power performance, good cycle performance and the like.

Description

Negative electrode composite material for high-power energy storage battery, and preparation method and application thereof
Technical Field
The invention relates to the technical field of battery materials, in particular to a negative electrode composite material for a high-power energy storage battery, and a preparation method and application thereof.
Background
The raw materials used for the current marketized anode material mainly comprise needle coke and petroleum coke, which have the problem of high cost, and the price fluctuation is large due to the influence of the market, so that the material cost stability of the anode material application side is influenced. The coal resources in China are abundant, the anthracite is used for preparing the anode material of the lithium ion battery, the high-efficiency clean utilization of coal can be realized, the production cost of the anode material is reduced, the added value of coal can be greatly improved, and the lithium ion battery has wide market application prospect, but the coal-based material has low specific capacity and low compaction density as the anode, the material is hard and influences the liquid absorption performance of the material, and the material is directly used as the anode material to influence the cycle performance and the high-rate charge-discharge performance, so that the internal structure and the outer coating of the material are required to be modified to improve the high-rate cycle performance of the material. For example, patent application number 201810057188.1 discloses a coal-based battery anode material, a preparation method and application thereof, wherein the preparation method comprises the steps of mixing bituminous coal with graphene to obtain a mixture, carbonizing and sintering to obtain the coal-based battery anode material, wherein the material is prepared by matching raw materials with graphene, so that the electrochemical properties of the material such as multiplying power and the like are improved, but the graphene only improves the electronic conductivity of the material, and the self carbon-based orientation of the material and the electronic conductivity of a shell of the material are not improved, so that the multiplying power lifting amplitude is not obvious. Therefore, development of a negative electrode composite material for a high-power energy storage battery is urgently required.
Disclosure of Invention
The invention adopts the following technical scheme:
in a first aspect, the invention provides a negative electrode composite material for a high-power energy storage battery, which is characterized by comprising a core-shell structure, wherein the core-shell structure comprises an inner core and an outer shell, the inner core is metal doped artificial graphite, the outer shell is a composite body of a bimetallic compound and amorphous carbon, and the mass of the outer shell is 2-10wt% of that of the negative electrode composite material.
According to the negative electrode composite material for the high-power energy storage battery, the metal is doped with the artificial graphite in the inner core, the bimetallic compound in the outer shell is matched, the resistivity of the material is reduced, and the specific capacity is improved and the orientation of the carbon-based material is improved by utilizing the bimetallic compound in the outer shell so as to improve the dynamic performance.
In another aspect, the present invention provides a method for preparing the anode composite material according to the first aspect, the method comprising the steps of:
s1, graphitizing oxidized anthracite at a low temperature of 2000-2600 ℃ for 6-24 hours, crushing and grading to obtain a graphite precursor material with a granularity of 5-20 mu m;
metal chloride in mass ratio: graphite precursor material: alkaline solution: aluminum-based coupling agent = 1-10:100:100-500:1-5, weighing each material, adding metal chloride into an organic solvent to prepare a metal chloride solution with the weight percent of 1-10%, then adding a graphite precursor material into the metal chloride solution, then dripping an alkaline solution and an aluminum-based coupling agent to uniformly disperse, carrying out hydrothermal reaction on the mixture, filtering the reacted mixture, and vacuum drying filter residues at the temperature of 80 ℃ for 24 hours to obtain a graphite precursor intermediate material;
s2, cerium acetate according to the mass ratio: cobalt chloride: ethylenediamine: alcohol solvent = 1-10:1-10:10-50: weighing 100-500, adding cerium acetate, cobalt chloride and ethylenediamine into alcohol solvent, and dispersing uniformly to obtain coating solution;
s3, graphite precursor intermediate materials are prepared according to mass ratio: coating liquid = 100:100-500, adding graphite precursor intermediate material into coating liquid, spray drying, and carbonizing at 700-1200 ℃ for 1-6h in inert atmosphere to obtain the bimetal/amorphous carbon coated coal-based negative electrode composite material.
Preferably, the preparation process of the oxidized anthracite coal in the step S1 is as follows: 1g of anthracite is weighed and placed in a three-neck flask, 10-30g of concentrated sulfuric acid with the concentration of 98wt percent is added, and then 1-5g of KMnO is added dropwise at the temperature of 30-80 DEG C 4 Reacting for 10-60min, filtering the reacted substance, washing the obtained solid substance with deionized water, and vacuum drying at 80deg.C for 24 hr to obtain oxidized anthracite.
Preferably, in step S1, the metal chloride is one or more of cobalt chloride, nickel chloride and ferric chloride; the alkaline solution is one or more of trimethylamine water solution, triethylamine water solution, tri-n-propylamine water solution and pyridine water solution with the concentration of 1-10wt%, and the water in the water solution is deionized water; the aluminum-based coupling agent is one or more of isopropyl dioleate acyloxy aluminate, triisopropyl aluminate, tribenzyl aluminate and trimethyl aluminate; the organic solvent is one or more of 1, 4-butanediol, propylene glycol and ethylene glycol.
Preferably, in the step S1, the reaction temperature of the hydrothermal reaction is 100-180 ℃ and the reaction time is 1-6h.
Preferably, the alcohol solvent in the step S2 is one or more of pentaerythritol, glycerol, xylitol and sorbitol.
Preferably, the inert atmosphere in step S3 is an argon atmosphere.
In yet another aspect, the present invention provides the use of a negative electrode composite material as described in another aspect in a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the negative electrode composite material for the high-power energy storage battery and the preparation method thereof, the chemical groups rich in the surface of the oxidized anthracite are utilized, active points are easy to form in the low-temperature graphitization process, the dynamic performance is improved, meanwhile, the active points are easier to combine with an aluminum-based coupling agent to form chemical bonds, and the impedance is reduced.
(2) According to the negative electrode composite material for the high-power energy storage battery and the preparation method thereof, the structural stability of the material core is improved through the aluminum-based coupling agent, and the material core has the advantages of good coating uniformity, strong bonding force with the core and the like through liquid phase coating, so that the cycle performance is improved.
(3) According to the negative electrode composite material for the high-power energy storage battery and the preparation method thereof, the specific capacity is improved through cerium oxide generated by the reaction, and the orientation of the carbon-based material is improved by combining the catalytic action of cobalt oxide generated by the reaction so as to improve the dynamic performance; the resistivity of the material is reduced by cladding the metal compound doped in the inner core and the bimetal coated in the outer shell.
(4) The negative electrode composite material for the high-power energy storage battery can be used in a lithium ion battery, and can improve the capacity and the cycle performance of the lithium ion battery.
Drawings
Fig. 1 is an SEM image of the bi-metal/amorphous carbon coated coal-based negative electrode composite material prepared in example 1.
Detailed Description
The following detailed description of the present invention will provide further details in order to make the above-mentioned objects, features and advantages of the present invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
Furthermore, the indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirements of the number of elements or components (i.e. the number of occurrences). Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component also includes the plural reference unless the amount is obvious to the singular reference.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The invention designs 3 examples and 2 comparative examples aiming at the negative electrode composite material for the high-power energy storage battery and a preparation method thereof.
Example 1:
a negative electrode composite material and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, graphitizing oxidized anthracite at 2400 ℃ for 12 hours, crushing and grading to obtain a graphite precursor material with the granularity of 10 m;
adding 5g of cobalt chloride into 100g of 1, 4-butanediol to prepare a cobalt chloride solution with the concentration of 5wt%, adding 100g of graphite precursor material into the cobalt chloride solution, then dropwise adding 300g of trimethylamine water solution with the concentration of 5wt% and 3g of isopropyl dioleoyl aluminate to disperse uniformly, carrying out hydrothermal reaction at 120 ℃ for 3 hours, filtering the reacted mixture, and vacuum-drying filter residues at the temperature of 80 ℃ for 24 hours to obtain the graphite precursor intermediate material;
s2, adding 5g of cerium acetate, 5g of cobalt chloride and 30g of ethylenediamine into 300g of pentaerythritol, and uniformly dispersing to obtain a coating liquid;
s3, adding 100g of graphite precursor intermediate material into 300g of coating liquid, spray drying, and carbonizing at 900 ℃ for 3 hours under an inert atmosphere of argon to obtain the bimetal/amorphous carbon coated coal-based negative electrode composite material.
Example 2:
a negative electrode composite material and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, graphitizing oxidized anthracite at a low temperature of 2000 ℃ for 24 hours, and crushing and grading to obtain a graphite precursor material with the granularity of 5 m;
adding 1g of nickel chloride into 100g of propylene glycol to prepare a nickel chloride solution with the concentration of 1wt%, adding 100g of graphite precursor material into the nickel chloride solution, then dripping 100g of triethylamine water solution with the concentration of 1wt% and 1g of triisopropyl aluminate to be uniformly dispersed, carrying out hydrothermal reaction at the temperature of 100 ℃ for 6 hours, filtering the reacted mixture, and vacuum drying filter residues at the temperature of 80 ℃ for 24 hours to obtain a graphite precursor intermediate material;
s2, adding 1g of cerium acetate, 1g of cobalt chloride and 10g of ethylenediamine into 100g of glycerol, and uniformly dispersing to obtain a coating liquid;
s3, adding 100g of graphite precursor intermediate material into 100g of coating liquid, spray drying, and carbonizing at 700 ℃ for 6 hours under an inert atmosphere of argon to obtain the bimetal/amorphous carbon coated coal-based negative electrode composite material.
Example 3:
a negative electrode composite material and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, graphitizing oxidized anthracite at a low temperature of 2600 ℃ for 6 hours, and crushing and grading to obtain a graphite precursor material with the granularity of 20 m;
adding 10g of ferric chloride into 100g of ethylene glycol to prepare 10wt% ferric chloride solution, adding 100g of graphite precursor material into the ferric chloride solution, then dripping 500g of 10wt% tri-n-propylamine water solution and 5g of tribenzyl aluminate to uniformly disperse, carrying out hydrothermal reaction at 180 ℃ for 1h, filtering the reacted mixture, and vacuum drying filter residues at 80 ℃ for 24h to obtain the graphite precursor intermediate material;
s2, adding 10g of cerium acetate, 10g of cobalt chloride and 50g of ethylenediamine into 500g of glycerol, and uniformly dispersing to obtain a coating liquid;
s3, adding 100g of graphite precursor intermediate material into 500g of coating liquid, spray drying, and carbonizing at 1200 ℃ for 1h under an inert atmosphere of argon to obtain the bimetal/amorphous carbon coated coal-based negative electrode composite material.
Comparative example 1:
except for the difference from example 1, cerium acetate and cobalt chloride were not added, and the other was the same as in example 1.
Comparative example 2:
except for the fact that cobalt chloride was not added, the procedure was the same as in example 1.
Wherein, in the above examples 1-3 and comparative examples 1-2, the preparation process of the oxidized anthracite coal in step S1 is as follows: 1g of anthracite is weighed and placed in a three-necked flask, 20g of concentrated sulfuric acid with the concentration of 98wt percent is added, and then 3g of KMnO is added dropwise at 50 DEG C 4 Reacting for 30min, filtering the reacted substance, washing the obtained solid substance with deionized water, and vacuum drying at 80 ℃ for 24h to obtain the oxidized anthracite.
Microcosmic morphology and performance test of materials
(1) Microcosmic morphology of the material:
fig. 1 is an SEM image of the bi-metal/amorphous carbon coated coal-based negative electrode composite material prepared in example 1, and it can be seen from fig. 1 that the negative electrode composite material is in a particle shape, the size distribution is reasonable, and the particle size is 8-12 m.
(2) Physical property test:
the negative electrode composites prepared in examples 1 to 3 and comparative examples 1 to 2 were subjected to tests of resistivity, powder compact density, specific surface area, particle size, graphitization degree and metal element content, and the test results are shown in table 1.
Resistivity test: the negative electrode composite materials are respectively pressed into blocks, and the resistivity of the negative electrode composite materials is tested by adopting a four-probe tester.
Powder compaction density test: and (3) using a powder compaction densitometer, placing 1g of powder into a fixed kettle, pressing by using 2T pressure, standing for 10s, calculating the volume after pressing, and calculating the powder compaction density.
In addition, the measurement of specific surface area, granularity and graphitization degree is tested according to the method of the national standard GB/T-24533-2019 lithium ion battery graphite negative electrode material.
The content of the metal element is measured according to an EDS method.
TABLE 1 physical Property test results of the negative electrode composite materials obtained in examples 1 to 3 and comparative examples 1 to 2
Index (I) Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2
Resistivity (Ω. M) 8.1*10 -8 5.7*10 -8 9.2*10 -8 6.6*10 -7 9.5*10 -7
Powder compaction Density (g/cm) 3 ) 1.59 1.51 1.62 1.51 1.47
Specific surface area (m) 2 /g) 1.85 1.77 1.91 1.41 1.71
Median diameter D50 (μm) 12.5 12.1 13.3 14.3 13.8
Degree of graphitization (%) 95.4 95.3 95.2 92.6 92.9
Content of metallic element (%) 9.2 2.3 16.1 8.4 10.3
As can be seen from table 1, the negative electrode composite materials prepared in examples 1 to 3 of the present invention have lower resistivity, larger specific surface area and higher graphitization degree compared to the negative electrode composite materials prepared in comparative examples 1 to 2, because the surface of the negative electrode composite material is doped with high metal oxide having electron conductivity, reducing the resistivity thereof; meanwhile, the metal oxide has a catalytic effect, and the graphitization degree of the material is improved in the carbonization process.
(3) Preparation and performance test of button cell:
adding binder, conductive agent and solvent into the negative electrode composite materials obtained in the examples 1-3 and the comparative examples 1-2 respectively, uniformly mixing to prepare negative electrode slurry, coating the negative electrode slurry on copper foil, drying, rolling and cutting to prepare a negative electrode plate; lithium sheet is used as counter electrode, and LiPF with l.2mol/L is adopted as electrolyte 6 EC+DEC, separator was a Celgard 2400 film, assembled into button cells in an argon-filled glove box, and button cells corresponding to examples 1-3 and comparative examples 1-2 were designated A1, A2, A3 and B1, B2, respectively.
The formula of the negative electrode slurry is as follows, and the negative electrode composite material comprises the following components in percentage by mass: SUPER carbon black: LA132 binder: secondary distilled water=95:1:4:220; in the electrolyte solvent, EC: DEC=1:1 according to the volume ratio.
The electrochemical performance of the prepared button cell is carried out on a Wuhan blue electric CT2001A type cell tester, and the first discharge specific capacity, the first efficiency and the multiplying power performance (1C/0.1C) of the button cell are tested in a charge-discharge voltage range of 0.005-2.0V and a charge-discharge rate of 0.1C. The test results are shown in Table 2.
Table 2 electrochemical performance test results of button cell
As is clear from table 2, the batteries A1, A2, A3 have larger initial discharge specific capacities, higher initial efficiencies, and better rate performance than the batteries B1, B2. The first discharge specific capacity of the button cell prepared by the negative electrode composite material obtained in the embodiment 1-3 of the invention is larger, the first efficiency is higher, and the cycle performance is better, which indicates that the negative electrode composite material obtained in the embodiment 1-3 of the invention has excellent performance. This is because cerium oxide produced by the reaction can increase specific capacity, and the catalytic action of cobalt oxide produced by the reaction can improve the orientation of the carbon-based material, thereby improving the dynamic performance and increasing the rate capability.
(4) Preparation and performance test of the soft package battery:
and (3) respectively adding a binder, a conductive agent and a solvent into the anode composite materials prepared in the examples 1-3 and the comparative examples 1-2, uniformly mixing to prepare anode slurry, coating the anode slurry on copper foil, drying, rolling and cutting to prepare the anode sheet. The formula of the negative electrode slurry is as follows, and the negative electrode composite material comprises the following components in percentage by mass: SUPER carbon black: LA132 binder: secondary distilled water=95:1:4:220; in the electrolyte solvent, EC: DEC=1:1 according to the volume ratio.
In preparing the positive electrode, the positive electrode material LiNi is prepared 1/3 Co 1/3 Mn 1/3 O 2 Adding binder, conductive agent and solvent into the ternary material, uniformly mixing to prepare anode slurry, coating the anode slurry on aluminum foil, drying, rolling and cutting to obtain the anode plate. The formula of the positive electrode slurry is as follows, and the positive electrode material comprises the following components in percentage by mass: SUPER carbon black: PVDF (polyvinylidene fluoride): secondary distilled water=97:1:2:110.
The electrolyte adopts l.3mol/L LiPF 6 The separator was a Celgard 2400 film to prepare a soft pack battery with a capacity of 2Ah, and the soft pack batteries corresponding to examples 1-3 and comparative examples 1-2 were designated as C1, C2, C3 and D1, D2, respectively.
Wherein, in the electrolyte solvent, EC: DEC=1:1 according to the volume ratio.
And then testing the cycle performance and the multiplying power performance of the soft package battery by adopting a Wuhan blue CT2001A battery tester. The test results are shown in Table 3.
Rate performance test conditions: the constant current ratio of the battery is tested by charging multiplying power of 1C/2C/3℃/5C, discharging multiplying power of 1C, voltage range of 2.8-4.2V and temperature of 25+/-3 ℃.
The cycle performance test conditions were: charging and discharging multiplying power is 2C/2C, and voltage range is 2.8-4.2V; the temperature is 25+/-3 ℃ and the cycle time is 500 weeks.
Table 3 results of electrochemical performance test of pouch cell
As can be seen from table 3, at different charging rates, the soft pack batteries C1, C2, and C3 all have higher constant current ratios than the soft pack batteries D1 and D2; after 500 times of circulation, compared with the soft package batteries D1 and D2, the soft package batteries C1, C2 and C3 have better circulation performance, which shows that the liquid absorption and retention capacity of the cathode electrode is obviously better than that of the comparative example; the reason is that the surface of the negative electrode composite material obtained in the embodiment 1-3 is coated with the bimetallic oxide, so that the conductivity of the material can be improved, the quick charge performance of the material is improved, namely the constant current ratio of the material is improved; meanwhile, the material has high specific surface area, improves the liquid retention performance of the material, and improves the cycle performance.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (8)

1. The negative electrode composite material for the high-power energy storage battery is characterized by comprising a core-shell structure, wherein the core-shell structure comprises an inner core and an outer shell, the inner core is metal doped artificial graphite, the outer shell is a composite body of a bimetallic compound and amorphous carbon, and the mass of the outer shell is 2-10wt% of that of the negative electrode composite material.
2. The method for producing a negative electrode composite material according to claim 1, characterized in that the method comprises the steps of:
s1, graphitizing oxidized anthracite at a low temperature of 2000-2600 ℃ for 6-24 hours, crushing and grading to obtain a graphite precursor material with a granularity of 5-20 mu m;
metal chloride in mass ratio: graphite precursor material: alkaline solution: aluminum-based coupling agent = 1-10:100:100-500:1-5, weighing each material, adding metal chloride into an organic solvent to prepare a metal chloride solution with the weight percent of 1-10%, then adding a graphite precursor material into the metal chloride solution, then dripping an alkaline solution and an aluminum-based coupling agent to uniformly disperse, carrying out hydrothermal reaction on the mixture, filtering the reacted mixture, and vacuum drying filter residues at the temperature of 80 ℃ for 24 hours to obtain a graphite precursor intermediate material;
s2, cerium acetate according to the mass ratio: cobalt chloride: ethylenediamine: alcohol solvent = 1-10:1-10:10-50: weighing 100-500, adding cerium acetate, cobalt chloride and ethylenediamine into alcohol solvent, and dispersing uniformly to obtain coating solution;
s3, graphite precursor intermediate materials are prepared according to mass ratio: coating liquid = 100:100-500, adding graphite precursor intermediate material into coating liquid, spray drying, and carbonizing at 700-1200 ℃ for 1-6h in inert atmosphere to obtain the bimetal/amorphous carbon coated coal-based negative electrode composite material.
3. The method according to claim 2, wherein the oxidizing anthracite coal in step S1 is prepared by the following steps: 1g of anthracite is weighed and placed in a three-neck flask, 10-30g of concentrated sulfuric acid with the concentration of 98wt percent is added, and then 1-5g of KMnO is added dropwise at the temperature of 30-80 DEG C 4 Reacting for 10-60min, filtering the reacted substance, washing the obtained solid substance with deionized water, and vacuum drying at 80deg.C for 24 hr to obtain oxidized anthracite.
4. The preparation method according to claim 2, wherein in step S1, the metal chloride is one or more of cobalt chloride, nickel chloride and ferric chloride; the alkaline solution is one or more of trimethylamine water solution, triethylamine water solution, tri-n-propylamine water solution and pyridine water solution with the concentration of 1-10wt%, and the water in the water solution is deionized water; the aluminum-based coupling agent is one or more of isopropyl dioleate acyloxy aluminate, triisopropyl aluminate, tribenzyl aluminate and trimethyl aluminate; the organic solvent is one or more of 1, 4-butanediol, propylene glycol and ethylene glycol.
5. The method according to claim 2, wherein in step S1, the hydrothermal reaction is carried out at a reaction temperature of 100 to 180 ℃ for a reaction time of 1 to 6 hours.
6. The preparation method according to claim 2, wherein the alcohol solvent in step S2 is one or more of pentaerythritol, glycerol, xylitol, and sorbitol.
7. The method according to claim 2, wherein the inert atmosphere in step S3 is an argon atmosphere.
8. The use of the negative electrode composite material according to claim 1 in a lithium ion battery.
CN202311101869.0A 2023-08-30 2023-08-30 Negative electrode composite material for high-power energy storage battery, and preparation method and application thereof Pending CN117080397A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311101869.0A CN117080397A (en) 2023-08-30 2023-08-30 Negative electrode composite material for high-power energy storage battery, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311101869.0A CN117080397A (en) 2023-08-30 2023-08-30 Negative electrode composite material for high-power energy storage battery, and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN117080397A true CN117080397A (en) 2023-11-17

Family

ID=88713138

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311101869.0A Pending CN117080397A (en) 2023-08-30 2023-08-30 Negative electrode composite material for high-power energy storage battery, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN117080397A (en)

Similar Documents

Publication Publication Date Title
WO2022166059A1 (en) Boron-doped resin-coated artificial graphite material
CN109119592B (en) Lithium titanate negative electrode piece, preparation method and lithium titanate battery
CN112467118B (en) Graphite composite material, preparation method thereof and lithium battery cathode
CN101714627A (en) Carbon nanotube/lithium iron phosphate composite positive electrode material and in situ preparation method thereof
CN114447305B (en) Multi-carbon-based quick-charge anode composite material and preparation method thereof
CN114122372B (en) Low-expansion silicon-carbon negative electrode material for lithium ion battery and preparation method thereof
CN114122391B (en) High-power graphite composite material and preparation method thereof
CN114408915B (en) High-energy-density graphite composite material and preparation method thereof
CN114613974B (en) Long-life quick-charging type lithium ion battery cathode material and preparation method thereof
CN115566170B (en) Preparation method of high-energy-density quick-charging lithium ion battery anode material
CN114655951B (en) Preparation method of lithium ion battery cathode material
CN112110448A (en) Nitrogen-doped carbon and nano-silicon composite anode material and preparation method thereof
JP2024532023A (en) Nitrogen-doped graphene-coated silicon carbon composites and their preparation methods and applications
CN114678505B (en) Sulfur-phosphorus co-doped hard carbon composite material and preparation method thereof
EP4145476A1 (en) Positive electrode of hybrid capacitor and manufacturing method therefor and use thereof
CN113066988B (en) Negative pole piece and preparation method and application thereof
CN115939361B (en) Copper phosphide doped hard carbon composite material and preparation method thereof
CN116130659A (en) Hard carbon composite material, material preparation method, electrode plate and battery
CN114162814B (en) Modification method of graphite
CN114122360A (en) High-energy-density quick-charging composite negative electrode material and preparation method thereof
CN117080397A (en) Negative electrode composite material for high-power energy storage battery, and preparation method and application thereof
CN115520851B (en) Preparation method of hard carbon-soft carbon-fast ion conductor composite material
CN115954465B (en) High-power hard carbon composite material and preparation method thereof
CN115911306B (en) High-energy-density graphite composite material and preparation method thereof
CN115513453A (en) Silver-doped hard carbon composite material, and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination