CN114695894A - High-capacity hard carbon fast-charging negative electrode material and preparation method and application thereof - Google Patents
High-capacity hard carbon fast-charging negative electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of lithium ion battery materials, and provides a high-capacity hard carbon fast-charging negative electrode material, and a preparation method and application thereof. The hard carbon fast-charging negative electrode material has a core-shell structure, the core is hard carbon doped with nitrogen and phosphorus, the shell comprises metal oxide and amorphous carbon, and the mass of the shell is 1-10% of that of the hard carbon fast-charging negative electrode material. The nitrogen source in the core of the hard carbon fast-charging negative electrode material has high electronic conductivity, the phosphorus source has high specific capacity, the metal oxide in the shell has high conductivity, and the core is matched with the shell, so that the obtained hard carbon fast-charging negative electrode material has good fast-charging performance, high energy density and first efficiency. Through the technical scheme, the problems of low first-time efficiency and low energy density of the hard carbon material in the related technology are solved.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a high-capacity hard carbon fast-charging cathode material and a preparation method and application thereof.
Background
Along with the improvement of the market on the requirements of high-energy-density battery on quick charge and low temperature, the lithium ion battery cathode material is required to have high energy density, and meanwhile, the quick charge and low temperature performance of the battery is also improved. The current marketable negative electrode material is mainly made of graphite materials, the specific capacity of the negative electrode material is 350-355mAh/g, the quick charging performance is less than or equal to 4C, and the charging capacity of the negative electrode material is reduced due to the layered structure of the negative electrode material. Although the market has the defects of low energy density, low primary efficiency and the like by improving the specific capacity of the material through doping of the material, such as patent CN 109768218A, the nitrogen-doped hard carbon lithium ion battery cathode material, the preparation method thereof, the lithium ion battery cathode sheet and the lithium ion battery are disclosed, the nitrogen source of the hard carbon lithium ion battery cathode material is choline chloride, and the flue gas generated by carbonizing the choline is alkaline in the high-temperature carbonization process and can generate a corrosion pore-forming effect on a main carbon supply source, so that the lithium storage performance is improved, but the polarization of the hard carbon lithium ion battery cathode material is larger, the voltage platform is high, the impedance of the hard carbon lithium battery cathode sheet is increased, and the primary efficiency is not improved.
Disclosure of Invention
The invention provides a high-capacity hard carbon fast-charging cathode material, and a preparation method and application thereof, and solves the problems of low first-time efficiency and low energy density of hard carbon materials in the related technology.
The technical scheme of the invention is as follows:
the invention provides a high-capacity hard carbon fast-charging negative electrode material which has a core-shell structure, wherein the core of the hard carbon fast-charging negative electrode material is hard carbon doped with nitrogen and phosphorus, the shell of the hard carbon fast-charging negative electrode material comprises metal oxide and amorphous carbon, and the mass of the shell is 1-10% of that of the hard carbon fast-charging negative electrode material.
According to the invention, the energy density of the hard carbon fast-charging cathode material is improved by doping the nitrogen-phosphorus complex, and the first efficiency and the fast-charging performance of the hard carbon fast-charging cathode material are improved by coating the metal oxide on the surface of the hard carbon fast-charging cathode material.
As a further feature, the hard carbon fast charging anode material has a particle size of 5 to 15 μm.
As a further feature, the kernel is formed by a mixture of a mass ratio of 100: (0.5-5): (0.5-5): (0.1-1) resin, a phosphorus source, a nitrogen source and a coupling agent.
Preferably, the resin comprises at least one of phenolic resin, furfural resin and epoxy resin.
Preferably, the source of phosphorus comprises at least one of phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate.
Preferably, the nitrogen source comprises at least one of urea, aniline, pyrrole, and thiophene.
Preferably, the coupling agent comprises at least one of aminotrimethoxy, aminopropyltriethoxysilane, gamma-aminoethylaminopropyltrimethoxysilane, gamma-aminoethylaminopropyltriethoxysilane, bis [3- (triethoxysilyl) propyl ] amine, bis (3-trimethoxysilylpropyl) amine, bis [3- (trimethoxysilyl) propyl ] ethylenediamine and bis [3- (triethoxysilyl) propyl ] ethylenediamine.
As a further feature, in the housing, the mass ratio of the metal oxide to the amorphous carbon is (10-30): (70-90).
Preferably, the metal oxide comprises Al2O3Porous MnO of2Porous CoO2Porous TiO 22Porous Fe2O3At least one of porous NiO and porous CuO.
Preferably, the pore size of the metal oxide is 10 to 100 nm.
Preferably, the pore size of the metal oxide is 50 nm.
The invention also provides a preparation method of the high-capacity hard carbon fast-charging cathode material, which comprises the following steps:
dissolving resin in a solvent A, adding a phosphorus source, a nitrogen source and a coupling agent, uniformly dispersing, and reacting to obtain a first reaction product;
sequentially filtering and drying the first reaction product, and then performing first carbonization treatment to obtain a hard carbon precursor material;
mixing metal oxide with a solvent B, adding the hard carbon precursor material and a dispersant, uniformly mixing, and reacting to obtain a second reaction product;
and filtering and drying the second reaction product, and then carrying out second carbonization treatment to obtain the hard carbon fast-charging cathode material.
As a further feature, the solvent a includes at least one of ethanol, acetylacetone, cyclohexane, isopropanol, acetic acid, dichloromethane, methyl ethyl ketone, and toluene.
Preferably, the solvent B comprises at least one of ethanol, acetylacetone, cyclohexane, isopropanol, acetic acid, dichloromethane, methyl ethyl ketone and toluene.
As a further characteristic, the reaction temperature is 50-200 ℃, and the reaction time is 1-6 h; the hydrothermal reaction temperature is 100-200 ℃, and the reaction time is 1-6 h.
Preferably, the temperature of the first carbonization treatment is 600-1000 ℃, and the time is 1-6 h.
Preferably, the temperature of the second carbonization treatment is 600-1200 ℃, and the time is 1-6 h.
Preferably, the second carbonization treatment is performed under an inert atmosphere.
Preferably, the inert atmosphere is a mixture of fluorine gas and argon gas in a volume ratio of 1: 10, in a mixed atmosphere.
As a further feature, the mass ratio of the metal oxide to the hard carbon precursor material to the dispersant is (1-5): 100: (0.5-2).
The invention also provides a negative electrode which comprises the hard carbon quick-charging negative electrode material.
The invention also provides a lithium ion battery which comprises the cathode.
The working principle and the beneficial effects of the invention are as follows:
1. according to the invention, the inner core of the hard carbon fast-charging negative electrode material is doped with a phosphorus source and a nitrogen source, the phosphorus source has high specific capacity, the nitrogen source has high electronic conductivity, the interaction of lone pair electrons and pi electrons is optimized by doping nitrogen atoms to improve the conductivity of the material, and the compatibility of the nitrogen source and the phosphorus source improves the lithium storage performance of the hard carbon fast-charging negative electrode material, so that the electronic conductivity and the specific capacity of the hard carbon fast-charging negative electrode material are improved; the shell comprises metal oxide and amorphous carbon, the surface of the inner core is coated with the metal oxide, the strong electronic conductivity of the metal oxide and the inertia of electrolyte are utilized, lithium ions consumed by a solid electrolyte interface film in the use process of the hard carbon fast-charging negative electrode material are reduced, the inner core doped with a nitrogen source and a phosphorus source is cooperatively matched with the shell comprising the metal oxide, and the first efficiency, the energy density and the fast-charging performance of the hard carbon fast-charging negative electrode material are obviously improved.
2. In the invention, the inner core of the hard carbon fast-charging negative electrode material is prepared from resin, a phosphorus source and a nitrogen source inner core coupling agent, the phosphorus source has good catalytic performance in the preparation process, the reaction process is accelerated, the lithium storage capacity of the hard carbon fast-charging negative electrode material is obviously improved through the catalytic pore-forming of the phosphorus source, the nitrogen source and the phosphorus source are connected through a chemical bond by the coupling agent, and the structural stability of the hard carbon fast-charging negative electrode material is further improved.
3. According to the preparation method of the hard carbon fast-charging cathode material, the hard carbon precursor material is prepared firstly, and then is subjected to hydrothermal reaction with the metal oxide and freeze drying to prepare the hard carbon fast-charging cathode material with the nanoscale hole structure, so that the hard carbon fast-charging cathode material has a high specific surface area and good lithium storage capacity, and the first efficiency, liquid absorption and retention capacity and rate capability of the hard carbon fast-charging cathode material are improved.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Fig. 1 is an SEM image of a hard carbon fast-charging anode material of example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any inventive step, are intended to be within the scope of the present invention.
Example 1
A preparation method of a high-capacity hard carbon fast-charging negative electrode material comprises the following steps:
(1) preparation of hard carbon precursor Material
Dissolving 100g of phenolic resin in 5000mL of cyclohexane to obtain a first solution;
adding 2g of phosphoric acid, 2g of urea and 0.5g of amino trimethoxy coupling agent into the first solution, and uniformly dispersing to obtain a first mixed solution;
transferring the first mixed solution into a reaction kettle, and reacting for 3 hours at the temperature of 100 ℃ to obtain a first reaction product;
filtering, spray drying and transferring the first reaction product into a tube furnace, heating to 800 ℃ under the inert atmosphere of argon, carbonizing for 3 hours, naturally cooling to room temperature, and crushing to obtain a hard carbon precursor material;
(2) preparation of hard carbon fast-charging cathode material
3g of porous Al2O3Adding the solution into 60mL of cyclohexane solution to obtain a second solution; porous Al2O3Has a particle diameter of 50 nm;
adding 100g of the hard carbon precursor material prepared in the step (1) and 1g of dodecyl trimethyl ammonium bromide into the second solution, and uniformly dispersing by ultrasonic to obtain a second mixed solution;
transferring the second mixed solution into a high-pressure reaction kettle, and reacting for 3 hours at the temperature of 150 ℃ to obtain a second reaction product;
filtering the second reaction product, freeze-drying at-40 ℃ for 48h, transferring to a tubular furnace, introducing argon inert atmosphere to remove air in the tube, introducing fluorine gas and argon at a volume ratio of 1: and (3) heating the mixed gas of 10 to 800 ℃, preserving the heat for 3 hours, and then naturally cooling to room temperature to obtain the hard carbon fast-charging cathode material.
Example 2
A preparation method of a high-capacity hard carbon fast-charging negative electrode material comprises the following steps:
(1) preparation of hard carbon precursor Material
Dissolving 100g of furfural resin in 10000mL of isopropanol to obtain a first solution;
adding 0.5g of ammonium phosphate, 0.5g of aniline and 0.1g of aminopropyltriethoxysilane into the first solution, and uniformly dispersing to obtain a first mixed solution;
transferring the first mixed solution into a reaction kettle, and reacting for 6 hours at the temperature of 50 ℃ to obtain a first reaction product;
filtering and spray-drying the first reaction product, transferring the first reaction product into a tubular furnace, heating to 600 ℃ in an inert atmosphere of argon gas, carbonizing for 6 hours, naturally cooling to room temperature, and crushing to obtain a hard carbon precursor material;
(2) preparation of hard carbon fast-charging cathode material
1g of porous MnO2Adding the solution into 60mL of isopropanol solution to obtain a second solution; porous MnO2The particle size of (A) is 10 nm;
adding 100g of the hard carbon precursor material prepared in the step (1) and 0.5g of dodecyl trimethyl ammonium bromide into the second solution, and uniformly dispersing by ultrasonic to obtain a second mixed solution;
transferring the second mixed solution into a high-pressure reaction kettle, and reacting for 6 hours at the temperature of 100 ℃ to obtain a second reaction product;
filtering the second reaction product, freeze-drying at-40 ℃ for 24h, transferring to a tubular furnace, introducing argon inert atmosphere to remove air in the tube, introducing fluorine gas and argon at a volume ratio of 1: and (3) heating the mixed gas of 10 to 600 ℃, preserving the heat for 6h, and then naturally cooling to room temperature to obtain the hard carbon fast-charging cathode material.
Example 3
A preparation method of a high-capacity hard carbon fast-charging negative electrode material comprises the following steps:
(1) preparation of hard carbon precursor Material
Dissolving 100g of epoxy resin in 2000mL of acetic acid to obtain a first solution;
adding 5g of ammonium dihydrogen phosphate, 5g of thiophene and 1g of gamma-aminoethyl aminopropyl triethoxysilane into the first solution, and uniformly dispersing to obtain a first mixed solution;
transferring the first mixed solution into a reaction kettle, and reacting at the temperature of 200 ℃ for 1h to obtain a first reaction product;
filtering and spray-drying the first reaction product, transferring the first reaction product into a tubular furnace, heating to 1000 ℃ in an inert atmosphere of argon gas, carbonizing for 1h, naturally cooling to room temperature, and crushing to obtain a hard carbon precursor material;
(2) preparation of hard carbon fast-charging cathode material
5g of porous TiO2Adding the solution into 50mL of acetic acid solution to obtain a second solution; porous TiO2The particle size of (A) is 100 nm;
adding 100g of the hard carbon precursor material prepared in the step (1) and 2g of dodecyl trimethyl ammonium bromide into the second solution, and uniformly dispersing by ultrasonic to obtain a second mixed solution;
transferring the second mixed solution into a high-pressure reaction kettle, and reacting for 1h at the temperature of 200 ℃ to obtain a second reaction product;
filtering the second reaction product, freeze-drying at-40 ℃ for 72h, transferring to a tubular furnace, introducing an argon inert atmosphere to remove air in the tube, and introducing fluorine gas and argon at a volume ratio of 1: and (3) heating the mixed gas of 10 to 1200 ℃, preserving the heat for 1h, and then naturally cooling to room temperature to obtain the hard carbon fast-charging cathode material.
Comparative example 1
Dissolving 100g of phenolic resin in 5000mL of cyclohexane to obtain a first solution;
transferring the first solution into a reaction kettle, and reacting for 3 hours at the temperature of 100 ℃ to obtain a first reaction product;
and filtering and spray-drying the first reaction product, transferring the first reaction product into a tubular furnace, heating to 800 ℃ in an inert atmosphere of argon gas, carbonizing for 3 hours, naturally cooling to room temperature, and crushing to obtain the hard carbon composite material.
Examples of the experiments
1. SEM test
The hard carbon fast-charging anode material prepared in example 1 is subjected to SEM test, and the result is shown in figure 1, and it can be seen from the figure that the hard carbon fast-charging anode material prepared in example 1 has a spheroidal structure, uniform size distribution and a particle size of 5-15 μm.
2. Physicochemical Properties and button cell test
The hard carbon fast-charging anode materials prepared in examples 1 to 3 and comparative example 1 were subjected to particle size, tap density, specific surface area, elemental analysis and specific capacity tests thereof. The test method comprises the following steps: GBT-245332009 graphite cathode material for lithium ion battery.
The hard carbon fast-charging negative electrode materials obtained in examples 1-3 and comparative example 1 are respectively assembled into button batteries A1, A2, A3 and B1; the preparation method comprises the following steps: adding a binder, a conductive agent and a solvent into the negative electrode material, stirring and pulping, coating the mixture on a copper foil, and drying and rolling the copper foil to obtain the copper-clad laminate. The used binders are LA132 binders, conductive agents SP, negative electrode materials are respectively hard carbon fast-charging negative electrode materials prepared in examples 1-3 and comparative example 1, and the solvent is secondary distilled water, and the proportion is as follows: and (3) anode material: SP: LA 132: 95g of secondary distilled water: 1 g: 4 g: 220mL, and preparing a negative pole piece; the electrolyte is LiPF6The battery simulation method comprises the following steps of (1: 1 volume ratio) and (1.3 mol/L concentration), wherein a metal lithium sheet is used as a counter electrode, a diaphragm is made of polyethylene PE, polypropylene PP or polyethylene propylene PEP composite film, a simulation battery is assembled in an argon-filled glove box, the electrochemical performance is carried out on a Wuhan blue electricity CT2001A type battery tester, the charging and discharging voltage range is 0.00V-2.0V, and the charging and discharging rate is 0.1C. The button cell battery is tested at the same time for multiplying power (2C/0.1C) and cycle performance (0.2C/0.2C, 200 times), and the test results are as follows:
table 1 results of physicochemical property tests of hard carbon fast-charging anode materials prepared in examples 1 to 3 and comparative example 1
| Numbering | Item | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| 1 | Particle size (D50, μm) | 7.6 | 7.9 | 7.5 | 9.1 |
| 3 | Tap density (g/cm)3) | 0.88 | 0.85 | 0.82 | 0.72 |
| 4 | Specific surface area (m)2/g) | 7.9 | 7.5 | 7.7 | 4.9 |
| 5 | Interlayer spacing (nm) | 0.389 | 0.387 | 0.381 | 0.368 |
| 6 | First discharge capacity (mAh/g) | 589 | 576 | 528 | 345 |
| 7 | First efficiency (%) | 86.2 | 86.4 | 85.6 | 82.3 |
| 8 | Multiplying power performance (2C/0.1C) | 92.5 | 91.6 | 90.1 | 84.3 |
| 9 | Cycle performance (capacity retention rate) | 94.7 | 93.3 | 92.9 | 89.3 |
As can be seen from table 1, compared with comparative example 1, the first discharge capacity, the first efficiency, the rate capability, and the cycle performance of the hard carbon fast-charging anode materials prepared in examples 1 to 3 are significantly improved, because in the present invention, the core of the hard carbon fast-charging anode material is doped with nitrogen and phosphorus, which improves the electronic conductivity and the specific capacity of the material, and simultaneously, the pores of the material are improved and the lithium storage capacity of the material is improved by the hydrothermal reaction and freeze-drying of the hard carbon precursor material and the porous metal oxide.
3. Soft package battery
The hard carbon fast-charging negative electrode materials prepared in examples 1-3 and comparative example 1 are used as negative electrode materials, a negative electrode piece is prepared, and a ternary material (LiNi) is used1/3Co1/3Mn1/3O2) As the positive electrode, LiPF6(the solvent is EC + DEC, the volume ratio is 1:1, and the concentration is 1.3mol/L) is used as electrolyte, the celegard2400 is used as a diaphragm to prepare 2Ah soft package batteries C1, C2, C3 and D, and then the ternary lithium battery is obtained, and the following tests are carried out, and the test results are shown in tables 2-3.
(1) Liquid absorption capacity of negative plate
TABLE 2 liquid-absorbing abilities of negative electrode sheets of examples 1 to 3 and comparative example 1
| Item | Imbibition speed (mL/min) | Liquid retention rate (24h electrolyte volume/0 h electrolyte volume) |
| Example 1 | 5.8 | 95.1％ |
| Example 2 | 4.6 | 94.3％ |
| Example 3 | 4.5 | 94.2％ |
| Comparative example 1 | 2.2 | 83.1％ |
As can be seen from table 2, the liquid absorbing and retaining capabilities of the negative electrode in examples 1 to 3 are significantly better than those of comparative example 1, and the reason for the analysis is that: in the invention, the hard carbon fast-charging cathode material prepared by a hydrothermal method and freeze drying has nanometer-scale holes and a high specific surface area, thereby improving the liquid absorption and retention capacity of the material.
(2) Rate capability
The rate performance of the soft package battery is tested, the charging and discharging voltage range is 2.75-4.2V, the temperature is 25 +/-3.0 ℃, the soft package battery is charged at 1.0C, 3.0C, 5.0C, 10.0C and 20.C, and the soft package battery is discharged at 1.0C, and the result is shown in table 3.
Table 3 rate of pouch cells of examples 1-3 and comparative example 1
As can be seen from the above table, the rate charge performance of the pouch cells in examples 1-3 is significantly better than that of comparative example 1, i.e., the pouch cells of examples 1-3 have shorter charge times, as analyzed for: the lithium ion migration is required in the battery charging process, the surface of the hard carbon fast-charging cathode material in the embodiments 1 to 3 is coated with the porous metal oxide with high conductivity, so that the power performance of the material is improved, and the rate capability of the material is improved due to the porous structure prepared by hydrothermal reaction in the preparation method.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The high-capacity hard carbon fast-charging negative electrode material is characterized in that the hard carbon fast-charging negative electrode material has a core-shell structure, the core of the hard carbon fast-charging negative electrode material is hard carbon doped with nitrogen and phosphorus, the shell of the hard carbon fast-charging negative electrode material comprises metal oxide and amorphous carbon, and the mass of the shell is 1-10% of that of the hard carbon fast-charging negative electrode material.
2. The high-capacity hard-carbon fast-charging negative electrode material as claimed in claim 1, wherein the particle size of the hard-carbon fast-charging negative electrode material is 5-15 μm.
3. The high-capacity hard-carbon fast-charging anode material as claimed in claim 1, wherein the core is composed of a mixture of, by mass, 100: (0.5-5): (0.5-5): (0.1-1) preparing the resin, the phosphorus source, the nitrogen source and the coupling agent;
preferably, the resin comprises at least one of phenolic resin, furfural resin and epoxy resin;
preferably, the source of phosphorus comprises at least one of phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, and ammonium dihydrogen phosphate;
preferably, the nitrogen source comprises at least one of urea, aniline, pyrrole, and thiophene;
preferably, the coupling agent comprises an amino coupling agent;
preferably, the amino coupling agent is at least one of aminotrimethoxy, aminopropyltriethoxysilane, gamma-aminoethylaminopropyltrimethoxysilane, gamma-aminoethylaminopropyltriethoxysilane, bis [3- (triethoxysilyl) propyl ] amine, bis (3-trimethoxysilylpropyl) amine, bis [3- (trimethoxysilyl) propyl ] ethylenediamine and bis [3- (triethoxysilyl) propyl ] ethylenediamine.
4. The high-capacity hard-carbon fast-charging anode material as claimed in claim 1, wherein the mass ratio of the metal oxide to the amorphous carbon in the shell is (10-30): (70-90);
preferably, the metal oxide comprises Al2O3Porous MnO of2Porous CoO2Porous TiO 22Porous Fe2O3At least one of porous NiO and porous CuO;
preferably, the pore size of the metal oxide is 10-100 nm;
5. the preparation method of the high-capacity hard carbon fast-charging anode material as claimed in any one of claims 1 to 4, characterized by comprising the following steps:
dissolving resin in a solvent A, adding a phosphorus source, a nitrogen source and a coupling agent, uniformly dispersing, and reacting to obtain a first reaction product;
sequentially filtering and drying the first reaction product, and then performing first carbonization treatment to obtain a hard carbon precursor material;
mixing metal oxide with a solvent B, adding the hard carbon precursor material and a dispersing agent, uniformly mixing, and carrying out hydrothermal reaction to obtain a second reaction product;
and filtering and drying the second reaction product, and then carrying out second carbonization treatment to obtain the hard carbon fast-charging cathode material.
6. The method for preparing the high-capacity hard carbon fast-charging anode material according to claim 5, wherein the solvent A comprises at least one of ethanol, acetylacetone, cyclohexane, isopropanol, acetic acid, dichloromethane, methyl ethyl ketone and toluene;
preferably, the solvent B comprises at least one of ethanol, acetylacetone, cyclohexane, isopropanol, acetic acid, dichloromethane, methyl ethyl ketone, and toluene.
7. The preparation method of the high-capacity hard carbon fast-charging anode material according to claim 5, characterized in that the reaction temperature is 50-200 ℃, and the reaction time is 1-6 h; the hydrothermal reaction temperature is 100-200 ℃, and the reaction time is 1-6 h;
preferably, the temperature of the first carbonization treatment is 600-1000 ℃, and the time is 1-6 h;
preferably, the temperature of the second carbonization treatment is 600-1200 ℃, and the time is 1-6 h;
preferably, the second carbonization treatment is performed under an inert atmosphere;
preferably, the inert atmosphere is a mixture of fluorine gas and argon gas in a volume ratio of 1: 10, in a mixed atmosphere.
8. The preparation method of the high-capacity hard-carbon fast-charging anode material as claimed in claim 5, wherein the mass ratio of the metal oxide to the hard-carbon precursor material to the dispersant is (1-5): 100: (0.5-2).
9. A negative electrode comprising the hard carbon fast-charging negative electrode material according to any one of claims 1 to 4.
10. A lithium ion battery comprising the negative electrode according to claim 9.
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