CN110620220A - Sn for potassium ion battery4P3/Ti3C2TxMXene composite negative electrode material - Google Patents

Sn for potassium ion battery4P3/Ti3C2TxMXene composite negative electrode material Download PDF

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CN110620220A
CN110620220A CN201910802729.3A CN201910802729A CN110620220A CN 110620220 A CN110620220 A CN 110620220A CN 201910802729 A CN201910802729 A CN 201910802729A CN 110620220 A CN110620220 A CN 110620220A
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mxene
negative electrode
electrode material
potassium ion
ion battery
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陈人杰
刘欢
屈雯洁
罗锐
黄茹玲
李丽
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Beijing University of Technology
Beijing Institute of Technology BIT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • H01M4/5805—Phosphides
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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

Abstract

The invention relates to Sn for a potassium ion battery4P3/Ti3C2TxA MXene composite anode material belongs to the technical field of potassium ion battery anode materials. The composite negative electrode material is composed of Sn4P3Nanoparticles and Ti3C2TxPrepared from MXene nanosheets by electrostatic self-assembly, Ti3C2TxThe MXene can improve Sn4P3Conductive property and buffer Sn4P3The volume change during potassium storage, so that the composite anode material has excellent cycle performanceAnd rate capability; in addition, the preparation method of the composite negative electrode material is simple, efficient, safe and low in cost, and is beneficial to popularization of Sn4P3The material is applied as a negative electrode material of a potassium ion battery.

Description

Sn for potassium ion battery4P3/Ti3C2TxMXene composite negative electrode material
Technical Field
The invention relates to Sn for a potassium ion battery4P3/Ti3C2TxA MXene composite anode material belongs to the technical field of potassium ion battery anode materials.
Background
The potassium ions can be used as current carriers to shuttle between the positive electrode material and the negative electrode material like lithium ions or sodium ions so as to complete the conversion between chemical energy and electric energy and further perform electrochemical energy storage. The potassium element has the advantages of low standard electrode potential, high resource storage amount, wide distribution and low cost, so the potassium ion battery is a novel low-cost high-performance electrochemical energy storage technology at present.
Sn as a negative electrode material of a high-performance potassium ion battery4P3The method is concerned by the advantages of high theoretical capacity, abundant resource reserves, low price and the like. However, Sn4P3Large volume change in the potassium storage process can cause rapid decay of cycling stability, and Sn4P3Low conductivity results in poor potassium storage rate performance, and these problems limit Sn4P3The material is used as a potassium storage negative electrode material.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides Sn for a potassium ion battery4P3/Ti3C2TxThe MXene composite negative electrode material is prepared from Sn4P3Nanoparticles and Ti3C2TxThe MXene nanosheet is prepared by electrostatic self-assembly and has excellent performanceCycle performance and rate performance.
The purpose of the invention is realized by the following technical scheme.
Sn for potassium ion battery4P3/Ti3C2TxThe MXene composite negative electrode material is prepared by adopting an electrostatic self-assembly method, and the specific method comprises the following steps:
sn is added4P3Preparing uniformly dispersed suspension from nano particles, surfactant and water, and mixing Ti3C2TxPreparing the MXene nanosheet and water into a solution; mixing the suspension and the solution, and then carrying out ultrasonic treatment at 0-50 ℃ for not less than 0.5h, wherein Sn is generated in the process4P3Assembly of nanoparticles to Ti by electrostatic interaction3C2TxCollecting solid product on MXene nanosheet, washing and drying to obtain Sn4P3/Ti3C2TxThe type MXene composite anode material.
Wherein Sn4P3Nanoparticles and Ti3C2TxThe mass ratio of the MXene nanosheets is (1-9): 1, and the mass of the surfactant is Sn4P310-20% of the mass of the nano particles, and the surfactant is at least one of thiourea, sodium dodecyl benzene sulfonate, hexadecyl ammonium bromide, P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer), Pluronic F127, Pluronic F108 and span 80.
Further, Sn is contained in the suspension4P3The concentration of the nano particles is 0.01 g/mL-2 g/mL; in solution, Ti3C2TxThe concentration of the MXene nano-sheet is 0.1-10 mg/mL.
Further, Sn4P3The particle diameter of the nano-particles is 10 nm-100 nm, and Ti3C2TxThe size of the MXene nano-sheet is 100 nm-5 μm.
Further, the temperature of the ultrasonic treatment is 25 ℃ to 30 ℃.
Furthermore, when the ultrasonic frequency is 40W, the ultrasonic time is 1 h-6 h.
Further, the surfactant is preferably thiourea.
Has the advantages that:
(1) sn according to the invention4P3/Ti3C2TxIn the MXene composite anode material, Ti3C2TxThe MXene can improve Sn4P3Conductive property and buffer Sn4P3Volume change during potassium storage, thereby increasing Sn4P3Cycle performance and rate performance during potassium storage;
(2)Ti3C2Txthe MXene is easily oxidized under the heating condition to produce titanium dioxide so as to reduce the electrochemical performance, and the surfactant is adopted as the stabilizer in the application, and the Sn is mixed by simple ultrasonic4P3Nanoparticles and Ti3C2TxSn prepared by electrostatic self-assembly of MXene nanosheets4P3The method has the advantages of simple operation, high efficiency, safety and low cost, and is favorable for popularizing Sn4P3The material is applied as a negative electrode material of a potassium ion battery.
Drawings
FIG. 1 is Sn prepared using example 24P3/Ti3C2TxAnd the rate performance diagram of the potassium ion battery assembled by the MXene composite negative electrode material.
FIG. 2 is Sn prepared using example 24P3/Ti3C2TxAnd (3) a cycle performance diagram of a potassium ion battery assembled by the MXene composite negative electrode material.
Detailed Description
The present invention is further illustrated by the following detailed description, wherein the processes are conventional unless otherwise specified, and the starting materials are commercially available from a public perspective unless otherwise specified.
In the following examples:
the potassium ion battery is assembled by the following steps: sn prepared in the example4P3/Ti3C2TxUniformly mixing the MXene composite negative electrode material, the conductive agent Super P and the binder CMC (carboxymethyl cellulose) according to the mass ratio of 8:1:1, taking water as a solvent to prepare a mixture, mixing the mixture into slurry, coating the slurry on a copper foil, and drying and cutting the pieces to obtain a working electrode; assembling a CR2025 type button half-cell by using 1M KFSI EC/PC (1:1) as electrolyte, potassium metal as a counter electrode and a reference electrode and glass fiber as a diaphragm;
Sn4P3reference to nanoparticles (Sn)4+xP3@ Amorphous Sn-P compositions as antibodies for Sodium-Ion Batteries with Low Cost, High Capacity, Long Life, and Superior RateCapability, Weijie Li, Shu-Lei Chou, Jia-ZHao Wang, Jung Ho Kim, Hua-Kun Liu, and Shi-Xue Dou, adv.Mater.,2014,26, 4037-4042), and adjusting the Sn by controlling the ball milling time4P3The particle size of the nanoparticles;
Ti3C2Txthe MXene Nanosheets were prepared by methods reported in the reference literature (Self-Assembly of transformation Metal Oxide Nanosheets for Fast and Stable Lithium Storage, Yi-TaoLiu, Peng Zhang, Ning Sun, Babak Anasori, Qi-ZHen Zhu, Huang Liu, Yury Gogotsi, andBi Xu, adv. Mater.,2018,1707334) and Ti of different sizes was obtained by varying the ultrasound time3C2TxMXene nanosheets.
Example 1
(1) 0.9g of Sn having an average particle diameter of 100nm4P3Nanoparticles and 9mg of thiourea (CH)4N2S) adding the mixture into 10mL of distilled water, and magnetically stirring the mixture at room temperature for 12 hours to form a suspension A;
10mg of Ti having an average size of 2 μm3C2TxAdding the MXene nanosheets into 100mL of distilled water, and uniformly stirring to form a solution B;
(2) adding 1mL of suspension A into 100mL of solution B, placing in an ultrasonic cleaner with ultrasonic frequency of 40W, and performing ultrasonic treatment at 25-30 ℃ for 3h, wherein Sn is generated in the process4P3Nanoparticles by electrostatic interactionIs arranged at Ti3C2TxType MXene nano-sheet;
(3) after ultrasonic treatment, collecting solid products, washing with water and ethanol for 3 times respectively, and finally drying in a vacuum box at 60 ℃ for 10 hours to obtain Sn4P3/Ti3C2TxThe type MXene composite anode material.
Sn prepared4P3/Ti3C2TxThe type MXene composite negative electrode material is assembled into a CR2025 type button half cell, and constant current charge and discharge test is carried out at 25 ℃, wherein the electrochemical window of the test is 0.01V-3.0V. When the battery is subjected to constant current charge and discharge test under the current of 50mA/g, the reversible capacity of the first week is 695.4 mAh/g. When the battery is subjected to constant-current charge and discharge test at the current density of 100mA/g, the reversible capacity in the first week is 654.9mAh/g, and the capacity retention rate after 100 cycles is 91%.
Example 2
(1) 1.8g of Sn having an average particle diameter of 10nm4P3Nanoparticles and 10mg of thiourea (CH)4N2S) adding the mixture into 10mL of distilled water, and magnetically stirring the mixture at room temperature for 12 hours to form a suspension A;
10mg of Ti having an average size of 10 μm3C2TxAdding the MXene nanosheets into 100mL of distilled water, and uniformly stirring to form a solution B;
(2) adding 0.5mL of the suspension A into 100mL of the solution B, placing the suspension in an ultrasonic cleaner with ultrasonic frequency of 40W, and performing ultrasonic treatment for 6h at 25-30 ℃, wherein Sn is generated in the process4P3The nanoparticles are assembled on Ti by electrostatic action3C2TxType MXene nano-sheet;
(3) after ultrasonic treatment, collecting solid products, washing with water and ethanol for 3 times respectively, and finally drying in a vacuum box at 60 ℃ for 10 hours to obtain Sn4P3/Ti3C2TxThe type MXene composite anode material.
Sn prepared4P3/Ti3C2TxThe type MXene composite negative electrode material is assembled into a CR2025 type button half cell,constant current charge and discharge test is carried out at 25 ℃, and the electrochemical window of the test is 0.01V-3.0V.
When the multiplying power performance of the battery is tested, the battery is firstly circulated for 10 times at a current density of 50mA/g, and then is respectively circulated for 10 times at current densities of 100mA/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g and 50mA/g in sequence, and the result is shown in figure 1. When the battery is subjected to constant-current charge and discharge tests at current densities of 50mA/g, 100mA/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g and 3A/g, the first-week reversible capacities at the corresponding current densities are 878.5mAh/g, 654.9mAh/g, 568.4mAh/g, 512.5mAh/g, 453.9mAh/g, 409.1mAh/g and 362.7mAh/g in sequence.
The cycle performance test result of the battery is shown in fig. 2, the battery is subjected to constant-current charge and discharge test under the current density of 100mA/g, the first-cycle reversible capacity is 728.1mAh/g, and the capacity retention rate after 100 cycles is 91%.
Example 3
(1) 0.86g of Sn having an average particle diameter of 50nm4P3Adding the nano particles and 10mg of hexadecyl ammonium bromide into 10mL of distilled water, and magnetically stirring at room temperature for 24 hours to form a suspension A;
10mg of Ti having an average size of 5 μm3C2TxAdding the MXene nanosheets into 100mL of distilled water, and uniformly stirring to form a solution B;
(2) adding 1mL of suspension A into 100mL of solution B, placing in an ultrasonic cleaner with ultrasonic frequency of 40W, and performing ultrasonic treatment at 25-30 ℃ for 6h, wherein Sn is generated in the process4P3The nanoparticles are assembled on Ti by electrostatic action3C2TxType MXene nano-sheet;
(3) after ultrasonic treatment, collecting solid products, washing with water and ethanol for 3 times respectively, and finally drying in a vacuum box at 60 ℃ for 10 hours to obtain Sn4P3/Ti3C2TxThe type MXene composite anode material.
Sn prepared4P3/Ti3C2TxThe CR2025 button half cell is assembled by the MXene composite anode material and is carried out with constant current at 25 DEG CAnd in the charge and discharge test, the electrochemical window of the test is 0.01V-3.0V. When the battery is subjected to constant current charge and discharge test under the current of 50mA/g, the reversible capacity of the first week is 622.1 mAh/g. When the battery is subjected to constant-current charge and discharge test at the current density of 100mA/g, the first-week reversible capacity is 530.3mAh/g, and the capacity retention rate after 100 cycles is 83%.
Example 4
(1) 0.86g of Sn having an average particle diameter of 50nm4P3Adding the nano particles and 10mg of Pluronic F127 into 10mL of distilled water, and magnetically stirring at room temperature for 12 hours to form a suspension A;
10mg of Ti having an average size of 3 μm3C2TxAdding the MXene nanosheets into 100mL of distilled water, and uniformly stirring to form a solution B;
(2) adding 1mL of suspension A into 100mL of solution B, placing in an ultrasonic cleaner with ultrasonic frequency of 40W, and performing ultrasonic treatment at 25-30 ℃ for 6h, wherein Sn is generated in the process4P3The nanoparticles are assembled on Ti by electrostatic action3C2TxType MXene nano-sheet;
(3) after ultrasonic treatment, collecting solid products, washing with water and ethanol for 3 times respectively, and finally drying in a vacuum box at 60 ℃ for 10 hours to obtain Sn4P3/Ti3C2TxThe type MXene composite anode material.
Sn prepared4P3/Ti3C2TxThe type MXene composite negative electrode material is assembled into a CR2025 type button half cell, and constant current charge and discharge test is carried out at 25 ℃, wherein the electrochemical window of the test is 0.01V-3.0V. When the battery is subjected to constant current charge and discharge test at the current of 50mA/g, the reversible capacity of the first week is 662.1 mAh/g. When the battery is subjected to constant-current charge and discharge test at the current density of 100mA/g, the reversible capacity in the first week is 593.5mAh/g, and the capacity retention rate after 100 cycles is 81%.
Example 5
(1) 1.72g of Sn having an average particle diameter of 100nm4P3Nanoparticles and 20mg Pluronic F127 were added to 10mL of distilled water and magnetically stirred at room temperatureAfter 24h, suspension A is formed;
10mg of Ti having an average size of 2 μm3C2TxAdding the MXene nanosheets into 100mL of distilled water, and uniformly stirring to form a solution B;
(2) adding 0.5mL of the suspension A into 100mL of the solution B, placing the suspension in an ultrasonic cleaner with ultrasonic frequency of 40W, and performing ultrasonic treatment for 12h at the temperature of between 25 and 30 ℃, wherein Sn is generated in the process4P3The nanoparticles are assembled on Ti by electrostatic action3C2TxType MXene nano-sheet;
(3) after ultrasonic treatment, collecting solid products, washing with water and ethanol for 3 times respectively, and finally drying in a vacuum box at 60 ℃ for 10 hours to obtain Sn4P3/Ti3C2TxThe type MXene composite anode material.
Sn prepared4P3/Ti3C2TxThe type MXene composite negative electrode material is assembled into a CR2025 type button half cell, and constant current charge and discharge test is carried out at 25 ℃, wherein the electrochemical window of the test is 0.01V-3.0V. When the battery is subjected to constant current charge and discharge test under the current of 50mA/g, the reversible capacity of the first week is 665.1 mAh/g. When the battery is subjected to constant-current charge and discharge test at the current density of 100mA/g, the reversible capacity in the first week is 553.5mAh/g, and the capacity retention rate after 100 cycles is 75%.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. Sn for potassium ion battery4P3/Ti3C2TxThe type MXene composite negative electrode material is characterized in that: the composite negative electrode material is prepared by adopting the following method,
sn is added4P3Preparing uniformly dispersed suspension from nano particles, surfactant and water, and mixing Ti3C2TxPreparing the MXene nanosheet and water into a solution; mixing the suspension and the solution, then carrying out ultrasonic treatment at 0-50 ℃ for not less than 0.5h, collecting a solid product, washing and drying to obtain Sn4P3/Ti3C2TxA type MXene composite anode material;
wherein Sn4P3Nanoparticles and Ti3C2TxThe mass ratio of the MXene nanosheets is (1-9): 1, and the mass of the surfactant is Sn4P310-20% of the mass of the nano particles, and the surfactant is at least one of thiourea, sodium dodecyl benzene sulfonate, hexadecyl ammonium bromide, P123, Pluronic F127, Pluronic F108 and span 80.
2. Sn for potassium ion battery according to claim 14P3/Ti3C2TxThe type MXene composite negative electrode material is characterized in that: in the suspension, Sn4P3The concentration of the nano particles is 0.01 g/mL-2 g/mL; in solution, Ti3C2TxThe concentration of the MXene nano-sheet is 0.1-10 mg/mL.
3. Sn for potassium ion battery according to claim 1 or 24P3/Ti3C2TxThe type MXene composite negative electrode material is characterized in that: sn (tin)4P3The particle diameter of the nano-particles is 10 nm-100 nm, and Ti3C2TxThe size of the MXene nano-sheet is 100 nm-5 μm.
4. Sn for potassium ion battery according to claim 14P3/Ti3C2TxThe type MXene composite negative electrode material is characterized in that: the temperature of ultrasonic treatment is 25-30 ℃.
5. Sn for potassium ion battery according to claim 14P3/Ti3C2TxType MXene compositeAn anode material, characterized in that: when the ultrasonic frequency is 40W, the ultrasonic time is 1 h-6 h.
6. Sn for potassium ion battery according to claim 14P3/Ti3C2TxThe type MXene composite negative electrode material is characterized in that: the surfactant is thiourea.
CN201910802729.3A 2019-08-28 2019-08-28 Sn for potassium ion battery4P3/Ti3C2TxMXene composite negative electrode material Pending CN110620220A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111710862A (en) * 2020-06-28 2020-09-25 山东大学 3D porous Sb/Ti for high-performance potassium ion battery3C2Preparation method of MXene composite material
CN112490426A (en) * 2020-11-27 2021-03-12 青岛大学 LiFePO4Preparation method of @ C/MXene composite material
CN113072045A (en) * 2021-03-26 2021-07-06 深圳市环保科技集团有限公司 Negative electrode active material, preparation method thereof, negative electrode material, negative electrode and potassium ion battery

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CN107895779A (en) * 2017-10-09 2018-04-10 中国科学院化学研究所 A kind of high power capacity kalium ion battery negative material and its preparation method and application

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DEPING LI 等: "Hierarchically porous carbon supported Sn4P3 as a superior anode material for potassium-ion batteries", 《ENERGY STORAGE MATERIALS》 *
HUAN LIU 等: "Electrostatic Self‑assembly of 0D–2D SnO2 Quantum Dots/Ti3C2Tx MXene Hybrids as Anode for Lithium‑Ion Batteries", 《NANO-MICRO LETT.》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111710862A (en) * 2020-06-28 2020-09-25 山东大学 3D porous Sb/Ti for high-performance potassium ion battery3C2Preparation method of MXene composite material
CN112490426A (en) * 2020-11-27 2021-03-12 青岛大学 LiFePO4Preparation method of @ C/MXene composite material
CN112490426B (en) * 2020-11-27 2021-12-14 青岛大学 LiFePO4Preparation method of @ C/MXene composite material
CN113072045A (en) * 2021-03-26 2021-07-06 深圳市环保科技集团有限公司 Negative electrode active material, preparation method thereof, negative electrode material, negative electrode and potassium ion battery

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Application publication date: 20191227