CN112010308B - Preparation method of surface modified titanium carbonitride battery negative electrode material - Google Patents
Preparation method of surface modified titanium carbonitride battery negative electrode material Download PDFInfo
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- 150000003608 titanium Chemical class 0.000 title claims abstract description 26
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
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- 238000000498 ball milling Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011812 mixed powder Substances 0.000 claims abstract description 7
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 24
- 229910052719 titanium Inorganic materials 0.000 claims description 19
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000010405 anode material Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000010406 cathode material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 7
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- 239000000463 material Substances 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
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- 239000000126 substance Substances 0.000 description 3
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- 229910000831 Steel Inorganic materials 0.000 description 2
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- 238000001308 synthesis method Methods 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/907—Oxycarbides; Sulfocarbides; Mixture of carbides
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- 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
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Abstract
The invention provides a preparation method of a surface modified titanium carbonitride battery cathode material, which comprises the steps of (1.4-2.2): (0.8-1.2): (0.8-1.2), adding the mixed powder into a self-propagating synthesis reaction kettle, performing high-temperature self-propagating reaction, performing ball milling treatment on the obtained block sample to obtain a powdery small particle sample, adding the powdery small particle sample into absolute ethyl alcohol, performing solvent ultrasonic treatment, centrifuging and drying to obtain titanium carbide powder, finally mixing the titanium carbide powder and sodium borohydride in a weight ratio of 1:4 under an argon atmosphere, heating, and cooling to room temperature to obtain the titanium carbide powder. The method disclosed by the invention is simple to operate, low in energy consumption, low in cost and environment-friendly, and the prepared surface-modified titanium carbonitride negative electrode material is high in specific capacity, good in conductivity, electrochemical activity, cycling stability and rate capability, and suitable for a lithium ion battery negative electrode.
Description
Technical Field
The invention relates to a preparation method of a surface modified titanium carbonitride battery negative electrode material, and belongs to the technical field of lithium ion battery negative electrode materials.
Background
The Barsoum team at the university of dreicher in the united states first developed the definition of "MAX phase" in 2000. MAX phase is called M n+1 AX n Phase (N is an integer of 1 to 3), M is a transition metal element, A is a third or fourth main group element, and X is C or N. At present, a large amount of compounds of MAX type are studied about Ti 3 SiC 2 And Ti is 3 AlC 2 For Ti 2 SC is less of a concern.As a member of MAX phase, ti 2 SC has special properties, the ratio of lattice parameters c/a is minimum, and the oxide SO is formed at room temperature once S is introduced into the A-site element 2 Is a gas. In addition, ti 2 The SC is used as a negative electrode material of the lithium ion battery, so that the lithium storage capacity is larger, and therefore, the synthesis and structure optimization research of the titanium carbonitride are necessary to be carried out. But of pure Ti 2 The interlayer combination of the SC is tighter, which is unfavorable for the deintercalation of lithium ions in the electrochemical process, and restricts the exertion of the lithium storage potential.
Disclosure of Invention
The invention aims to solve the defects and provide a preparation method of the surface modified titanium carbonitride battery anode material, which is simple to operate, low in energy consumption and low in cost.
Technical proposal
The invention takes titanium powder, sulfur powder and graphite powder as raw materials, and obtains Ti rich in defects and high in activity through a self-propagating high-temperature synthesis method 2 SC powder, submicron Ti prepared by solvent ultrasonic stripping 2 And the SC nano sheet is used for constructing defects such as oxygen vacancies and the like on the surface of the nano sheet, adjusting the oxygen content on the surface of the material, reducing the diffusion energy barrier of lithium ions and promoting the diffusion of the lithium ions, so that the deintercalation of the lithium ions is more complete, and the lithium storage performance of the SC nano sheet is optimized. The specific scheme is as follows:
the preparation method of the surface modified titanium carbide battery cathode material comprises the following steps:
(1) Titanium powder, sulfur powder and graphite powder are mixed according to the following proportion (1.4-2.2): (0.8-1.2): (0.8-1.2) ball milling and mixing to obtain mixed powder;
(2) Adding the mixed powder into a self-propagating synthesis reaction kettle, and performing high-temperature self-propagating reaction to obtain a block sample;
(3) Ball milling is carried out on the block sample to obtain a powdery small particle sample;
(4) Adding the powdery small particle sample into absolute ethyl alcohol for solvent ultrasonic treatment, and then centrifuging and drying to obtain titanium carbonitride powder;
(5) And mixing titanium carbonitride powder and sodium borohydride in a weight ratio of 1:4 under the argon atmosphere, heating, and cooling to room temperature to obtain the surface modified titanium carbonitride battery anode material.
Further, in the step (1), the rotating speed is 300r/min during ball milling, the ball milling time is 2-5h, and the relative humidity is controlled to be less than or equal to 60% during powder mixing.
In the step (2), the high-temperature self-propagating reaction is carried out under the condition of inert gas argon, and the air pressure in the reaction kettle is controlled to be 0.24-0.26MPa.
Further, in the step (2), the reaction temperature of the high-temperature self-propagating reaction is 95-105 ℃ and the reaction time is 3-5min.
Further, in the step (3), ball milling is carried out under the argon condition, the ball milling rotating speed is 400r/min, and the ball milling time is 2h;
further, in the step (4), every 1g of the powdery small particle sample was added to 30ml of absolute ethanol.
Further, in the step (4), the rotational speed of the centrifugation is 400-600r/min.
Further, in the step (4), the drying temperature is 55-65 ℃.
Further, in the step (5), the heating temperature is 350-400 ℃, the time is 2 hours, and the heating rate is 5 ℃/min.
The surface modified titanium carbonitride battery negative electrode material is applied to the preparation of lithium ion batteries.
The invention has the beneficial effects that: the invention takes titanium powder, sulfur powder and graphite powder as raw materials, and obtains Ti rich in defects and high in activity through a self-propagating high-temperature synthesis method 2 SC powder, followed by solvent ultrasonic stripping to prepare submicron Ti 2 And the SC nano sheet is used for constructing defects such as oxygen vacancies and the like on the surface of the nano sheet, adjusting the oxygen content on the surface of the material, reducing the diffusion energy barrier of lithium ions and promoting the diffusion of the lithium ions, so that the deintercalation of the lithium ions is more complete, and the lithium storage performance of the SC nano sheet is optimized. Compared with other preparation schemes, the method disclosed by the invention is simple to operate, low in energy consumption, low in cost and environment-friendly, and the prepared surface-modified titanium carbonitride negative electrode material is high in specific capacity, good in conductivity, electrochemical activity, cycling stability and rate capability and suitable for a negative electrode of a lithium ion battery.
Drawings
FIG. 1 is an XRD pattern of the titanium carbonitride powder obtained in example 1;
FIG. 2 is an SEM image of titanium carbonitride powder obtained in example 1;
FIG. 3 is an XRD pattern of the surface-modified titanium carbonitride battery negative electrode materials produced in example 1, comparative example 1 and comparative example 2;
fig. 4 is an SEM image of the surface-modified titanium carbonitride battery negative electrode material produced in example 1, comparative example 1 and comparative example 2.
Detailed Description
The technical scheme of the invention is further described below with reference to the attached drawings and specific embodiments.
Example 1
The preparation method of the surface modified titanium carbide battery cathode material comprises the following steps:
(1) Titanium powder, sulfur powder and graphite powder are mixed according to a ratio of 2:1:1, controlling the ball material ratio in the tank to be 4:1, the mass ratio of small, medium and large steel balls to be 3:4:3, introducing argon as a protective gas, performing ball milling, controlling the relative humidity to be less than or equal to 60%, setting the parameters to be 300r/min, and performing ball milling for 3 hours to obtain mixed powder;
(2) Adding the mixed powder into a self-propagating synthesis reaction kettle, introducing argon as a protective gas, maintaining the gas pressure in the reaction kettle at 0.26MPa after three times of gas washing, opening low-pressure ignition, and performing high-temperature self-propagating reaction (100 ℃ for 5 min) to obtain a block sample;
(3) Adding a block-shaped sample into a ball milling tank after roughly crushing, controlling the ball-material ratio in the tank to be 4:1, the mass ratio of small, medium and large steel balls to be 3:4:3, introducing argon as a shielding gas, setting parameters to be 400r/min, ball milling for 2 hours, and taking raw materials with 200-300 meshes under the screen to obtain a powdery small particle sample;
(4) Adding a powdery small particle sample into absolute ethyl alcohol (30 ml of absolute ethyl alcohol is added into each 1g of powdery small particle sample), performing solvent ultrasonic treatment, centrifuging for 20min at 500r/min, performing suction filtration on the centrifuged upper liquid, drying the powder obtained after suction filtration in a vacuum drying oven, setting the parameters to 55 ℃ for 4h, and performing air release after the vacuum drying oven is cooled to room temperature to obtain titanium carbonitride powder;
SEM and XRD tests were carried out on the powder obtained in the step (4), FIG. 1 is an XRD pattern of the titanium carbonitride powder obtained in the example 1, FIG. 2 is an SEM pattern of the titanium carbonitride powder, and comparison of PDF cards with FIGS. 1 and 2 shows that submicron Ti was successfully synthesized 2 SC。
(5) And (3) mixing titanium carbonitride powder and sodium borohydride in a weight ratio of 1:4 under argon atmosphere, heating to 400 ℃ (controlling the heating rate to be 5 ℃/min), preserving heat for 2 hours, and cooling to room temperature to obtain the surface modified titanium carbonitride battery anode material.
The negative electrode material prepared in example 1 was subjected to battery assembly. Raw materials are prepared according to the mass ratio: acetylene black: PVDF=8:1:1 is prepared and then is put into a grinding tank to be ground for 1.5h-2h until the PVDF=8:1:1 is uniform viscous liquid, the PVDF=8:1:1 is uniformly smeared on a copper sheet, and the copper sheet is put into a vacuum drying oven to be dried under the condition that the drying temperature is 100 ℃ and the drying time is 12h. And after the drying is finished, taking out the copper sheet, and putting the copper sheet into a glove box to assemble the lithium battery. After the battery is assembled, the battery is placed under the environment of 25 ℃ and constant humidity for 2-4 hours, so that substances in the battery are fully activated, and then the electrochemical performance test is carried out. The test results show that: the surface modified titanium carbonitride battery negative electrode material prepared in the embodiment 1 has the specific capacity of 172.50mAh/g for the first time under the current density of 400mA/g, and is excellent in cycle performance, and the specific capacity is increased to 505.66mAh/g when the material is cycled for 1000 circles. This illustrates the surface oxygen vacancy-rich Ti prepared in example 1 2 The SC is used as a cathode material of a lithium battery and has good lithium storage performance.
Comparative example 1
Modifying the step (5) as follows: under argon atmosphere, independently heating the titanium carbonitride powder to 400 ℃ (controlling the temperature rising rate to 5 ℃/min) and preserving the temperature for 2 hours.
The remainder was the same as in example 1.
The negative electrode material prepared in comparative example 1 was subjected to battery assembly. Raw materials are prepared according to the mass ratio: acetylene black: PVDF=8:1:1 is prepared and then is put into a grinding tank to be ground for 1.5h-2h until the PVDF=8:1:1 is uniform viscous liquid, the PVDF=8:1:1 is uniformly smeared on a copper sheet, and the copper sheet is put into a vacuum drying oven to be dried under the condition that the drying temperature is 100 ℃ and the drying time is 12h. And after the drying is finished, taking out the copper sheet, and putting the copper sheet into a glove box to assemble the lithium battery. After the battery is assembled, the battery is placed under the environment of 25 ℃ and constant humidity for 2-4 hours, so that substances in the battery are fully activated, and then the electrochemical performance test is carried out.
Electrochemical performance test results: the specific capacity of the surface modified titanium carbonitride battery cathode material prepared in comparative example 1 is 84.69mAh/g when the surface modified titanium carbonitride battery cathode material is charged for the first time under the current density of 400mA/g, and the specific capacity is increased to 308.46mAh/g when the surface modified titanium carbonitride battery cathode material is circulated for 1000 circles.
Comparative example 2
Modifying the step (5) as follows: in air, the titanium carbonitride powder is independently heated to 400 ℃ (the temperature rising rate is controlled to be 5 ℃/min) and is kept for 2 hours.
The remainder was the same as in example 1.
The negative electrode material prepared in comparative example 2 was subjected to battery assembly. Raw materials are prepared according to the mass ratio: acetylene black: PVDF=8:1:1 is prepared and then is put into a grinding tank to be ground for 1.5h-2h until the PVDF=8:1:1 is uniform viscous liquid, the PVDF=8:1:1 is uniformly smeared on a copper sheet, and the copper sheet is put into a vacuum drying oven to be dried under the condition that the drying temperature is 100 ℃ and the drying time is 12h. And after the drying is finished, taking out the copper sheet, and putting the copper sheet into a glove box to assemble the lithium battery. After the battery is assembled, the battery is placed under the environment of 25 ℃ and constant humidity for 2-4 hours, so that substances in the battery are fully activated, and then the electrochemical performance test is carried out.
Electrochemical performance test results: the specific charge capacity of the surface-modified titanium carbonitride battery prepared in comparative example 2 was 147.98mAh/g in the first cycle at a current density of 400mA/g, and increased to 212.25mAh/g after 1000 cycles.
XRD and SEM tests were conducted on the surface-modified titanium carbonitride battery anode materials produced in example 1, comparative example 1 and comparative example 2, and the results were shown in FIGS. 3 and 4, wherein FIG. 4a shows example 1, FIG. 4b shows comparative example 1, and FIG. 4c shows the surface-modified titanium carbonitride battery anode material produced in comparative example 2. As can be seen from a comparison of fig. 3 and fig. 1, the XRD pattern of the titanium carbonitride powder subjected to surface modification by heating is substantially identical to the main peak position of the XRD pattern of the titanium carbonitride powder before modification, and it can be seen that the titanium carbonitride powder still retains its original crystal form after heating, and only the surface state is changed, wherein the negative electrode material of example 1 is subjected to sodium borohydride co-heating and argon atmosphere heating, and the peaks of the XRD pattern become more pronounced, indicating that the heating promotes crystallization of the material and reduction of the surface oxide, while the peaks of the XRD pattern of comparative example 2 heated in air are significantly weakened, indicating that the powder surface oxide film becomes thickened after heating. As can be seen from a comparison of fig. 4 and 2, the shape and size of the titanium carbonitride powder after surface modification by heating substantially corresponds to those of the titanium carbonitride powder before modification, indicating that the crystal structure of the titanium carbonitride was not changed by heating, and as can be seen from fig. 4a, the surface of the powder obtained in example 1 was roughened, indicating that the surface oxide thereof was reduced, and as can be seen from fig. 2, the surface of fig. 4b was smoother, indicating that an oxide film was formed on the surface of the powder by heating in air.
Claims (7)
1. The preparation method of the surface modified titanium carbide battery anode material is characterized by comprising the following steps of:
(1) Titanium powder, sulfur powder and graphite powder are mixed according to the following proportion (1.4-2.2): (0.8-1.2): (0.8-1.2) ball milling and mixing to obtain mixed powder;
(2) Adding the mixed powder into a self-propagating synthesis reaction kettle, and performing high-temperature self-propagating reaction to obtain a block sample;
(3) Ball milling is carried out on the block sample to obtain a powdery small particle sample;
(4) Adding the powdery small particle sample into absolute ethyl alcohol for solvent ultrasonic treatment, and then centrifuging and drying to obtain titanium carbonitride powder;
(5) Mixing titanium carbonitride powder and sodium borohydride in a weight ratio of 1:4 under argon atmosphere, heating, and cooling to room temperature to obtain a surface modified titanium carbonitride battery negative electrode material;
in the step (2), the high-temperature self-propagating reaction is carried out under the condition of inert gas argon, the air pressure in the reaction kettle is controlled to be 0.24-0.26MPa, the reaction temperature of the high-temperature self-propagating reaction is 95-105 ℃, and the reaction time is 3-5min;
in the step (3), ball milling is carried out under the argon condition, the ball milling rotating speed is 400r/min, and the ball milling time is 2h.
2. The method for preparing a surface-modified titanium carbonitride battery negative electrode material according to claim 1, wherein in the step (1), the rotation speed is 300r/min during ball milling, the ball milling time is 2-5h, and the relative humidity is controlled to be less than or equal to 60% during powder mixing.
3. The method for producing a surface-modified titanium carbonitride battery negative electrode material according to claim 1, wherein in the step (4), each 1g of the powdery small particle sample is added to 30ml of absolute ethanol.
4. The method for preparing a surface-modified titanium carbonitride battery negative electrode material according to claim 1, wherein in the step (4), the rotational speed of the centrifugation is 400-600r/min.
5. The method for preparing a surface-modified titanium carbonitride battery negative electrode material according to claim 1, wherein in the step (4), the drying temperature is 55-65 ℃.
6. The method for producing a surface-modified titanium carbonitride battery negative electrode material according to any one of claims 1 to 5, wherein in the step (5), the heating temperature is 350 to 400 ℃, the time is 2 hours, and the heating rate is 5 ℃/min.
7. Use of the surface modified titanium carbonitride battery negative electrode material prepared by the preparation method of any one of claims 1 to 6 for preparing lithium ion batteries.
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| CN104326748A (en) * | 2014-09-11 | 2015-02-04 | 哈尔滨师范大学 | Method for self propagating high temperature synthesis of titanium-sulfur-carbon powder material |
| CN108075135A (en) * | 2017-12-26 | 2018-05-25 | 盐城工学院 | A kind of preparation method for mixing vanadium carbon titanium sulfide cell negative electrode material and its resulting materials and application |
| CN110921639A (en) * | 2019-11-29 | 2020-03-27 | 江苏大学 | Preparation method of nano titanium carbonitride powder |
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| US10756345B2 (en) * | 2017-04-20 | 2020-08-25 | Auburn University | Electrochemical systems comprising MXenes and MAX phase compositions and methods of using the same |
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| CN104326748A (en) * | 2014-09-11 | 2015-02-04 | 哈尔滨师范大学 | Method for self propagating high temperature synthesis of titanium-sulfur-carbon powder material |
| CN108075135A (en) * | 2017-12-26 | 2018-05-25 | 盐城工学院 | A kind of preparation method for mixing vanadium carbon titanium sulfide cell negative electrode material and its resulting materials and application |
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