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CN-121974347-A - MAX phase negative electrode material with metal defect of lithium ion battery, and preparation method and application thereof

CN121974347ACN 121974347 ACN121974347 ACN 121974347ACN-121974347-A

Abstract

The application discloses a metal defect MAX phase negative electrode material of a lithium ion battery, and a preparation method and application thereof, and belongs to the technical field of lithium ion battery materials. The application combines a self-propagating high-temperature solid phase one-step method to simply and efficiently prepare a large quantity of double transition metal materials, and obtains the metal-defect MAX phase material through HF etching. Compared with the traditional MAX phase material, the material prepared by the application has excellent long-cycle stability, and can effectively relieve the problem of volume expansion in the charge and discharge process, thereby prolonging the service life of the battery. The material can promote the rapid transmission of electrons and lithium ions, and further improve the overall performance of the battery.

Inventors

  • XU JIANGUANG
  • SHI JIAJIA
  • BAI DONGLONG
  • DENG BIN
  • ZHANG MINGLONG
  • CHENG ZITONG
  • ZHENG XUE

Assignees

  • 上海第二工业大学

Dates

Publication Date
20260505
Application Date
20260122

Claims (10)

  1. 1. The preparation method of the MAX phase negative electrode material with the metal defect of the lithium ion battery is characterized by comprising the following steps of: firstly, adding transition metal powder M1, transition metal powder M2, sulfur powder and carbon powder into a ball milling tank, and performing ball milling to obtain a first mixed system; Step two, the first mixed system is put into a graphite crucible with the inner surface coated with boron nitride and pressed into blocks, and then the blocks are put into a self-propagating high-temperature reaction kettle, and under the protection of inert gas, the block materials synthesized through the self-propagating high-temperature reaction are the second mixed system; Step three, putting the second mixed system into a ball mill for crushing, and sieving to obtain a solid solution powder material which is a third mixed system; And fourthly, etching the third mixed system material by using hydrofluoric acid, washing the third mixed system material to be neutral after finishing, adding an intercalation agent for intercalation, respectively carrying out ultrasonic treatment or cell disruption treatment after intercalation, and centrifuging, collecting, freeze-drying or carrying out suction filtration and drying after finishing to obtain the metal defect MAX phase anode material.
  2. 2. The method according to claim 1, wherein in the first step, the transition metal powder M1 is Ti, the transition metal powder M2 is one selected from Cr and Nb, and the molar ratio of the transition metal powder M1, the transition metal powder M2, the sulfur powder and the carbon powder is 4/3:2/3:1:1.
  3. 3. The preparation method according to claim 1, wherein in the first step, the ball milling speed is 300-400rpm/min for 4-6 hours, and in the third step, the ball milling speed is 300-400rpm/min for 4-6 hours, and the sieving parameter is 400 mesh sieve.
  4. 4. The preparation method according to claim 1, wherein the etching treatment method comprises the steps of adding a third mixed system material into hydrofluoric acid, and heating in an oil bath; the material of the third mixed system and the dosage ratio of hydrofluoric acid are 2g to 40mL, the concentration of the hydrofluoric acid is 40%, the etching time is 72h, the temperature of the oil bath is set to 45 ℃, and the rotating speed of the oil bath is 700rpm/min.
  5. 5. The preparation method of claim 1, wherein the intercalation agent is one of absolute ethyl alcohol, dimethyl sulfoxide, tetramethyl ammonium hydroxide and tetrabutyl ammonium hydroxide, the intercalation parameter is set to be 6 hours, and the stirring speed is 1000rpm/min.
  6. 6. The method according to claim 1, wherein in the fourth step, the ratio of the third mixed system material, hydrofluoric acid, tetramethylammonium hydroxide, and the intercalating agent is 2 g/40 ml.
  7. 7. The method according to claim 1, wherein in the step four, the cell disruption treatment is carried out at a power of 105W and at a temperature of 10-15 ℃ for 80min by using a cell disrupter, the ultrasonic treatment is carried out at a temperature of 15 ℃ for 12h, and the freeze-drying parameter is a freeze-dryer temperature of-64 ℃ for 48 h.
  8. 8. The metal-deficient MAX-phase anode material prepared by the method of any one of claims 1 to 7.
  9. 9. A method for preparing a negative electrode plate by using the metal defect MAX phase negative electrode material according to claim 8, which is characterized in that the metal defect MAX phase negative electrode material, a conductive agent and an adhesive are uniformly mixed, N-methyl pyrrolidone is used as a solvent to prepare negative electrode slurry, then the negative electrode slurry is uniformly scraped on a Cu foil, and the solvent is removed by heating in a vacuum drying oven, so that the negative electrode plate is obtained.
  10. 10. The method of claim 9, wherein the mass ratio of the metal defect MAX phase material negative electrode material, the conductive agent, and the adhesive is 8:1:1.

Description

MAX phase negative electrode material with metal defect of lithium ion battery, and preparation method and application thereof Technical Field The invention belongs to the technical field of MAX phase materials, and particularly relates to a MAX phase negative electrode material with metal defects of a lithium ion battery, and a preparation method and application thereof. Background Intheresearchfieldofnegativeelectrodematerialsoflithiumionbatteries,MAXphasematerialsarehotspotsinrecentyears,MAXphasematerialsarenanolamellarternarycompoundswithhexagonalcrystalstructures,andthematerialsintegrateexcellentperformancesofmetalsandceramicsduetotheuniquechemicalbondingcharacteristics,namelystrongcovalent/ionicbondsinM-XlayersandweakmetalbondsbetweenM-Alayers. The ceramic has the core advantages of high electrical conductivity, high thermal conductivity, good processability and thermal shock resistance similar to metals, and high modulus, high temperature resistance, oxidation resistance and corrosion resistance of ceramics, and the unique combination of properties makes the ceramic have extremely high application value in extreme environments. Although MAX phase materials have great potential, traditional MAX phase crystal structures are extremely compact and complete, the surface energy is low, and the chemical active sites are insufficient. The defect engineering becomes a key path for breaking through the performance bottleneck of MAX phase, and the shuttle channel of lithium ions in the material is improved through the metal site defects artificially introduced in the crystal lattice, so that the capacity and the cycle life of the battery are improved. In recent years, the focus of research has shifted to non-stoichiometric and vacancy ordered structures, such as defects in artificially created a-atoms by acid etching or selective high temperature removal techniques. By introducing metal defects (such as A-site defects), the reaction energy barrier can be obviously reduced, the ion migration rate can be improved, and breakthroughs are made in the aspects of Hydrogen Evolution Reaction (HER) and metal ion battery cathodes. Disclosure of Invention The invention aims to develop a metal defect MAX phase negative electrode material of a lithium ion battery, a preparation method and application thereof. According to the invention, the MAX phase material with the defects of the metal layer is obtained by etching the double transition metal, the material adopts a simple and efficient preparation process, can obtain a high-purity product, has excellent electrochemical performance, provides a new solution for the cathode material of the lithium ion battery, and has a wide application prospect. The preparation method of the metal defect MAX phase anode material of the lithium ion battery comprises the following steps: firstly, adding transition metal powder M1, transition metal powder M2, sulfur powder and carbon powder into a ball milling tank, and performing ball milling to obtain a first mixed system; Preferably, in the first step, the transition metal powder M1 is Ti, and the transition metal powder M2 is selected from one of Cr and Nb. Preferably, in the first step, the mole ratio of the transition metal powder M1, the transition metal powder M2, the sulfur powder and the carbon powder is 4/3:2/3:1:1. Preferably, in the first step, the ball milling rotating speed is 300-400rpm/min, and the time is 4-6h. Step two, the first mixed system is put into a graphite crucible with the inner surface coated with boron nitride and pressed into blocks, and then the blocks are put into a self-propagating high-temperature reaction kettle, and under the protection of inert gas, the block materials synthesized through the self-propagating high-temperature reaction are the second mixed system; Preferably, in the second step, the inert gas is argon. Step three, putting the second mixed system into a ball mill for crushing, and sieving to obtain a solid solution powder material which is a third mixed system; Preferably, in the third step, the ball mill is set with parameters of 300-400rpm/min and 4-6h. Screening parameters are 400 mesh screen. Etching the third mixed system material by using hydrofluoric acid, washing to be neutral after finishing, adding an intercalation agent for intercalation, respectively carrying out ultrasonic treatment or cell disruption treatment after intercalation, and centrifuging, collecting, freeze-drying or suction-filtering and drying after finishing to obtain the metal defect MAX phase material M1 4/3M22/3-x SC, wherein X is 0< X <1/2. Preferably, in the fourth step, the acid etching treatment method comprises the steps of adding the third mixed system material into hydrofluoric acid, then placing the mixture into an oil bath for heating, wherein the etching time is 72 hours, the temperature of the oil bath is set to be 45 ℃, and the rotating speed of the oil bath is set to be 700rpm/min. Preferably, the