CN107946576A - A kind of high magnification graphite cathode material and preparation method thereof, lithium ion battery - Google Patents
A kind of high magnification graphite cathode material and preparation method thereof, lithium ion battery Download PDFInfo
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of high magnification graphite cathode material and preparation method thereof, lithium ion battery.The high magnification graphite cathode material includes graphite kernel and is coated on the hard carbon material layer of graphite core surface, and the hard carbon material layer is doped with lithium nitride.High magnification graphite cathode material provided by the invention, modification is doped to hard carbon material using lithium nitride, on the one hand the close lithium of kernel and hard carbon material can be utilized, establishes the structural nexus of kernel and clad, improves the compatibility and structural stability of kernel and clad；On the other hand, lattice defect can be formed in carbon-coating using lithium doping is nitrogenized, improve the mobility of electronics, increase storage lithium binding site, the interlamellar spacing of carbon-based material can also be increased at the same time, the migration rate of lithium ion is improved, which is had the characteristics that structural stability is good, interlamellar spacing is big, storage lithium binding site is more, lithium ion and electron transfer rate are fast, can be improved the fast charge ability of lithium ion battery with high degree.
Description
Technical field
The invention belongs to the preparation field of graphite negative electrodes material, and in particular to a kind of high magnification graphite cathode material and its
Preparation method, lithium ion battery.
Background technology
With the fast development of electric automobile, the lithium ion battery that energy density is big, charge/discharge rates are fast is more subject to city
The favor of field.Negative material is an important factor for restricting lithium ion battery fast charge capability improving.The negative material of existing market
Mainly based on graphite material, although it has necessarily in structural stability, structural order, cost, cycle performance etc.
Advantage, but the small rate charge-discharge ability deviation for determining graphite cathode of the interlamellar spacing of material in itself, when quick charge deposits
In " analysis lithium " risk.It is one of method for improving negative material fast charge ability that graphite material, which is modified,.
Application publication number is that the patent of CN102306796A discloses a kind of composite graphite negative electrode material, which bears
Pole material includes native graphite kernel and is coated on the clad of native graphite core surface, and the clad is phenolic resin carbon
The hard carbon formed after change.The composite graphite negative electrode material carries out coating modification using hard carbon to native graphite, to a certain extent
The characteristics of big hard carbon material interlamellar spacing, structural disorder can be utilized, improves the charge-discharge performance of lithium ion battery, but in fast charge energy
It still is apparent not enough in power.
The content of the invention
It is an object of the invention to provide a kind of high magnification graphite cathode material, deposited so as to solve existing graphite cathode material
Fast charge energy force difference the problem of.
Second object of the present invention is the preparation method for providing above-mentioned high magnification graphite cathode material.
Third object of the present invention is to provide the lithium ion battery using above-mentioned high magnification graphite cathode material.
To achieve the above object, the technical solution adopted in the present invention is：
A kind of high magnification graphite cathode material, including graphite kernel and the hard carbon material layer for being coated on graphite core surface,
The hard carbon material layer is doped with lithium nitride.
High magnification graphite cathode material provided by the invention, hard carbon material is doped modification, a side using lithium nitride
Face can utilize the close lithium of kernel and hard carbon material, establish the structural nexus of kernel and clad, improve kernel and clad
Compatibility and structural stability；On the other hand, lattice defect can be formed in carbon-coating using nitrogenizing lithium doping, improves electronics
Mobility, increase storage lithium binding site, while the interlamellar spacing of carbon materials can also be increased, improve the migration rate of lithium ion；Together
When, nitridation lithium material in itself or lithium fast-ionic conductor and has certain electronic conduction ability concurrently, is conducive to improve moving for electronics
The capacity for moving speed and material plays；Under the collective effect of above-mentioned factor, the graphite cathode material have structural stability it is good,
The characteristics of interlamellar spacing is big, storage lithium binding site is more, lithium ion and electron transfer rate are fast, and then lithium ion can be improved with high degree
The fast charge ability of battery.
Preferably, the hard carbon material layer is also doped with N, B, S, Cl or F.By the doping of the elements such as N, B, S, Cl, F,
The electron conduction of negative material is can further improve, further improves the rate charge-discharge performance and its capacity hair of negative material
Wave.
The thickness of the hard carbon material layer is 100~500nm.
Technical solution is used by above-mentioned high magnification graphite cathode material：
A kind of preparation method of high magnification graphite cathode material, comprises the following steps：
1) hard carbon presoma, passivation of lithium powder, graphite are added in nonaqueous solvents and is uniformly mixed, it is spray-dried, before preparation
Drive body particle；
2) granular precursor and nitrogen are reacted, prepares nitridation lithium doping presoma, then will nitrogenize lithium doping presoma
Carry out carburizing sintering, to obtain the final product.
Step 1) is the preparation process of granular precursor, which is mixed by liquid phase, be spray-dried, by hard carbon forerunner
Body, passivation of lithium powder are coated on graphite kernel.
Further to obtain more preferably liquid phase mixed effect, it is preferred that first hard carbon presoma is mixed with nonaqueous solvents, then
Add passivation of lithium powder to be uniformly mixed, obtain covering liquid；Then graphite is added in covering liquid and be uniformly mixed, recycle spray drying
Prepare granular precursor.
The nonaqueous solvents is alcohols solvent.Preferably, the alcohols solvent is ethanol.Hard carbon presoma can conveniently dissolve
In ethanol.Nonaqueous solvents used in the step can avoid reacting with passivation of lithium powder, can also use ability
Other organic solvents known to domain, such as ether, dichloromethane.
Hard carbon presoma is the precursor polymer for preparing hard carbon material, its can be prepare hard carbon material routine it is organic
Polymer, it is preferred that the hard carbon presoma for phenolic resin, epoxy resin, furfural resin, one kind in acrylic resin or
A variety of combinations.Passivation of lithium powder is commercially available customary commercial.Preferably, the graphite is native graphite.
The hard carbon presoma, passivation of lithium powder, the mass ratio of graphite are (1~10)：(0.1~1)：100.Hard carbon forerunner
Body, passivation of lithium powder can cause covered effect not good enough or influence follow-up doping effect, the quality of three above or below above range
Ratio controls within the above range, you can obtains the granular precursor that particle diameter distribution is uniform, covered effect is good.
Step 2) is to react to realize the doping of lithium nitride using the lithium in granular precursor and nitrogen, then utilizes carbon
Change sintering and prepare hard carbon.
In step 2), the reaction is granular precursor is reacted with nitrogen using electric spark deposition.The step is
Using electric spark deposition technology, electric discharge generation electric spark, triggers the presoma on metallic matrix between electrode and metallic matrix
Particle is reacted with nitrogen.Preferably, during electric spark deposition, the power for producing electric spark is 600~800W, electricity
It is 500~1000Hz to press as 80~120V, frequency.
Nitridation lithium doping presoma is prepared by electric spark deposition technology, has that synthesis rate is fast, process control, uniformity
The advantages that high, suitable for industrialized production.
In step 2), it first will nitrogenize lithium doping presoma and dopant containing N, B, S, Cl or F element mix, then carry out institute
State carburizing sintering.The dopant containing N, B, S, Cl or F element is pyrroles, pyridine, thiophene, aniline, N2H4, silicon fluoride, boron nitrogen
Benzene or carbon tetrachloride.
Preferably, the mixing is to nitrogenize the ethanol solution mixing of lithium doping presoma and dopant.It is further preferred that
In the ethanol solution of dopant, the mass concentration of dopant is 1~10%.
The carburizing sintering carries out under ammonia atmosphere.Preferably, the carburizing sintering is to keep the temperature 2 at 600~800 DEG C
~12h.It is sintered using ammonia atmosphere, can reacts ammonia and the hydroxycarboxyl group on carbon-based material surface, nitrogen is mixed
It is miscellaneous in carbon surface.It is sintered using above-mentioned sintering condition, sintering temperature is low, technique is simple, the quality stability of products obtained therefrom
It is good.
On the basis of above-mentioned high magnification graphite cathode material, phase is prepared using the known technology of those skilled in the art
The cathode pole piece and lithium ion battery answered.Such as mixed with negative material, conductive agent, binding agent and solvent, prepare negative material slurry
Then negative material slurries are prepared cathode pole piece by liquid coated on copper foil through drying, molding.Afterwards using ternary material as just
Pole, with LiPF6Solution is electrolyte, using PE, PP or composite membrane as membrane, according to the prior art be assembled into various forms of lithiums from
Sub- battery.
Using the lithium ion battery of above-mentioned high magnification graphite cathode material, first discharge capacity and efficient first, circulation
Performance, high rate performance, cryogenic property are improved comprehensively.
Brief description of the drawings
Fig. 1 is the SEM figures of the high magnification graphite cathode material of embodiment 1；
Fig. 2 is the multiplying power charge graph of the lithium ion battery of embodiment 1.
Embodiment
Embodiments of the present invention are described further with reference to specific embodiment.In following embodiments, phenolic aldehyde tree
The softening point of fat is 64-68 DEG C, electrical conductivity≤2 μ s/cm, hydroxyl equivalent 103-107g/eq, model PF-8606, purchased from Ji
Southern holy well sea Butterworth Chemical Co., Ltd..The epoxide equivalent of epoxy resin is 185-197g/eq, hydrolyzes chlorine≤300ppm, fusing point
For 138-146 DEG C, chlorion≤300ppm, model SQE-101, purchased from Jinan holy well sea Butterworth Chemical Co., Ltd..Furfural
The softening point of resin is 105-125 DEG C, hydroxyl equivalent 70-120g/eq, electrical conductivity≤1 μ s/cm, model INT-105, purchase
From Jinan holy well sea Butterworth Chemical Co., Ltd..The model Li-1 of passivation of lithium powder, purchased from Tianjin China Energy Lithium Co., Ltd..
Embodiment 1
The high magnification graphite cathode material of the present embodiment, including graphite kernel and the hard carbon material for being entrained in graphite core surface
The bed of material, for the hard carbon material layer doped with lithium nitride, the thickness of hard carbon material layer is 100nm.
The preparation method of the high magnification graphite cathode material of the present embodiment, is prepared using following steps：
1) 5g phenolic resin is added in 500mL ethanol, 0.5g passivation of lithium powder is added after being uniformly dispersed, disperseed again equal
It is even to obtain covering liquid；100g native graphites are added in covering liquid afterwards and are uniformly mixed, it is spray-dried to prepare presoma
Grain；
2) in a nitrogen atmosphere, granular precursor is reacted with nitrogen using electric spark deposition, prepare lithium nitride and mix
Miscellaneous presoma；The power for producing electric spark is 750W, voltage 100V, output power 800Hz；
3) lithium doping presoma will be nitrogenized and is soaked in 3h in the chromium solution (solvent is ethanol) that mass concentration is 5%, mistake
Filter residue, is then transferred in tube furnace by filter, drying, under ammonia atmosphere, is warming up to 700 DEG C of insulation 6h, and stopping is passed through ammonia,
Be passed through argon gas again and be naturally cooling to room temperature, to obtain the final product.
The lithium ion battery of the present embodiment, the negative material of 9g the present embodiment, 0.5g conductive agents SP, 0.5gLA132 are glued
Agent, the mixing of 220mL water are tied, prepares negative material slurries；By negative material slurries coated on copper foil, it is made through drying, roll-in
Anode；Then with ternary material (LiNi1/3Co1/3Mn1/3O2) it is cathode, with the LiPF of 1.3mol/L6(solvent is by EC, DEC for solution
By volume 1:1 mixes) be electrolyte, celegard2400 is membrane, by the prior art be assembled into 10Ah Soft Rolls lithium from
Sub- battery.
Embodiment 2
The high magnification graphite cathode material of the present embodiment, including graphite kernel and the hard carbon material for being entrained in graphite core surface
The bed of material, for the hard carbon material layer doped with lithium nitride and element S, the thickness of hard carbon material layer is 300nm.
The preparation method of the high magnification graphite cathode material of the present embodiment, is prepared using following steps：
1) 1g epoxy resin is added in 500mL ethanol, 0.1g passivation of lithium powder is added after being uniformly dispersed, disperseed again equal
It is even to obtain covering liquid；100g native graphites are added in covering liquid afterwards and are uniformly mixed, it is spray-dried to prepare presoma
Grain；
2) in a nitrogen atmosphere, granular precursor is reacted with nitrogen using electric spark deposition, prepare lithium nitride and mix
Miscellaneous presoma；The power for producing electric spark is 600W, voltage 80V, output power 500Hz；
3) lithium doping presoma will be nitrogenized and is soaked in 1h in the thiophene solution (solvent is ethanol) that mass concentration is 1%, mistake
Filter residue, is then transferred in tube furnace by filter, drying, under ammonia atmosphere, is warming up to 600 DEG C of insulation 12h, stopping is passed through ammonia
Gas, then be passed through argon gas and be naturally cooling to room temperature, to obtain the final product.
The lithium ion battery of the present embodiment, using the negative material of the present embodiment, the method for reference implementation example 1 prepares 10Ah
Soft bag lithium ionic cell.
Embodiment 3
The high magnification graphite cathode material of the present embodiment, including graphite kernel and the hard carbon material for being entrained in graphite core surface
The bed of material, for the hard carbon material layer doped with lithium nitride, the thickness of hard carbon material layer is 500nm.
The preparation method of the high magnification graphite cathode material of the present embodiment, is prepared using following steps：
1) 10g furfural resins are added in 500mL ethanol, 1g passivation of lithium powder is added after being uniformly dispersed, disperseed again equal
It is even to obtain covering liquid；100g native graphites are added in covering liquid afterwards and are uniformly mixed, it is spray-dried to prepare presoma
Grain；
2) in a nitrogen atmosphere, granular precursor is reacted with nitrogen using electric spark deposition, prepare lithium nitride and mix
Miscellaneous presoma；The power for producing electric spark is 800W, voltage 120V, output power 1000Hz；
3) lithium doping presoma will be nitrogenized and is soaked in 12h in the aniline solution (solvent is ethanol) that mass concentration is 10%,
Filter residue, is then transferred in tube furnace by filtering, drying, under ammonia atmosphere, is warming up to 800 DEG C of insulation 2h, stopping is passed through ammonia
Gas, then be passed through argon gas and be naturally cooling to room temperature, to obtain the final product.
The lithium ion battery of the present embodiment, using the negative material of the present embodiment, the method for reference implementation example 1 prepares 10Ah
Soft bag lithium ionic cell.
In the other embodiment of the high magnification graphite cathode material of the present invention, hard carbon presoma can be by embodiment 3
Method carries out equivalent replacement using acrylic resin, using boron pyridine, hydrazine, carbon tetrachloride, silicon fluoride or pyridine to dopant
Carry out equivalent replacement, the suitable negative material of availability.
Comparative example 1
The graphite cathode material of comparative example 1, is prepared using following steps：
1) 5g phenolic resin is added in 500mL ethanol, after being uniformly dispersed, addition 1g lithium nitrides, which are uniformly mixed, to be wrapped
Covering liquid；100g native graphites are added in covering liquid afterwards, it is spray-dried, prepare nitridation lithium doping presoma；
2) nitridation lithium doping presoma is transferred in tube furnace, under ammonia atmosphere, is warming up to 700 DEG C of insulation 6h, stops
Only be passed through ammonia, then be passed through argon gas and be naturally cooling to room temperature, to obtain the final product.
Using the graphite cathode material of comparative example 1, the method for reference implementation example 1 prepares 10Ah soft bag lithium ionic cells.
Comparative example 2
The graphite cathode material of comparative example 2, is prepared using following steps：
1) 5g phenolic resin is added in 500mL ethanol, covering liquid is obtained after being uniformly dispersed；Native graphite is added afterwards
Enter into covering liquid, it is spray-dried to prepare granular precursor；
2) granular precursor is soaked in the chromium solution (solvent is ethanol) of 5wt%, filtering, drying afterwards will filters
Slag is transferred in tube furnace, under ammonia atmosphere, is warming up to 700 DEG C of insulation 6h, stopping is passed through ammonia, then is passed through argon gas and drops naturally
Warm to room temperature, to obtain the final product.
Using the graphite cathode material of comparative example 2,1 method of reference implementation example prepares 10Ah soft bag lithium ionic cells.
Test example 1
This test example investigates the exterior appearance of the high magnification graphite cathode material of embodiment 1, and the results are shown in Figure 1 for it, by
Figure understands that the appearance of the high magnification graphite cathode material of embodiment 1 is in spherical, and clad dense uniform, particle diameter is at 8-15 μm.
Test example 2
This test example according to《GB/T 24533-2009 silicon/carbon/graphite in lithium ion batteries class negative materials》Defined method measure is each
Specific surface area, tap density and the interlamellar spacing of the negative material of embodiment and comparative example, wherein interlamellar spacing are material surface hard carbon
The testing result of material.
The negative material, 0.5g conductive agents SP, 0.5g LA132 binding agents for weighing each embodiments of 9g and comparative example respectively add
It is added in the deionized water of 220mL, coated on diaphragm is made on copper foil after stirring evenly, then using lithium piece as anode,
Celegard2400 is membrane, and concentration is the LiPF of 1mol/L6(solvent is 1 by volume ratio to solution:1 EC, DMC is mixed)
For electrolyte, button cell is assembled into the glove box that oxygen and water content are below 0.1ppm, then in blue electric tester
The discharge capacity first of each button cell of upper test and first efficiency, with the rate charge-discharge of 0.1C during detection, 0.05V~
In the voltage range of 2.0V, circulation stops after 3 weeks, and testing result is as shown in table 1.
1 each embodiment of table and the negative material of comparative example and the performance of button cell compare
As shown in Table 1, the negative material of embodiment relative to comparative example have more excellent efficiency first and gram
Capacity, the reason is that the lattice defect that nitridation lithium doping produces can bring more lithium binding sites, increases the layer of hard carbon material
Spacing, while nitrogenize lithium material and can promote the transmission of lithium ion in itself, so as to improve the gram volume and storage lithium of negative material
Performance.The negative material that it can be seen from the data such as specific surface area, tap density, interlamellar spacing by negative material prepared by the present invention
Specific surface area and tap density with bigger, interlamellar spacing further increase, and above-mentioned factor is conducive to further improve anode material
The gram volume of material.
Test example 3
Cycle performance, high rate performance and the low temperature that this test example detects the Soft Roll ion battery of each embodiment and comparative example are put
Electrical property, wherein, when high rate performance is tested, charging current is respectively 1C, 5C, 10C, 20C, 25C, 30C, discharge current 1C,
Voltage range is 3.0-4.1V, constant current ratio=constant-current charge capacity/(constant-current charge capacity+constant-voltage charge capacity).Cycle performance
During test, charging and discharging currents 3C/3C, voltage range 3.0-4.1V, cycle-index are 500 times.Low temperature performance detects
When, charging current 1C, discharge current 1C, discharge test temperature are respectively 25 DEG C, 0 DEG C, -20 DEG C, -30 DEG C.Testing result
As shown in table 2 and table 3.
The multiplying power charging performance contrast of the soft bag lithium ionic cell of 2 each embodiment of table and comparative example
From the detection data of table 2, soft bag lithium ionic cell prepared by embodiment has the constant current ratio of higher, shows
More preferably rapid charging performance, it can be seen that, method using the present invention is modified hard carbon material, can optimize stone with high degree
The big multiplying power charging performance of black negative material, so as to meet the needs of electric automobile is to rapid charge characteristic.
Fig. 2 is that battery multiplying power charging of the soft bag lithium ionic cell of embodiment 1 under 1C, 5C, 10C, 20C, 25C, 30C is bent
Line, as shown in Figure 2 embodiment battery there is the constant current ratio of higher, i.e. fast charge ability.
The low temperature performance and cycle performance of the soft bag lithium ionic cell of 3 each embodiment of table and comparative example
The soft bag lithium ionic cell of embodiment is in low temperature discharge and its capacity retention ratio side it can be seen from the result of table 3
Face is substantially better than comparative example, the reason is that being doped modification to hard carbon material using the method for the present invention, can improve hard carbon
The interlamellar spacing of material, increases the transmission rate of the lithium ion under negative material cryogenic conditions, and then is conducive to improve negative material
Low temperature discharge conservation rate and big circulation performance.
It can be seen that lithium ion battery provided by the invention has rapid charging performance concurrently, low temperature is put with reference to the result of table 2 and table 3
Electrical property and big circulation performance, lithium nitride are doped in hard carbon material and can play raising lithium by impurity element modification
Ion transportation and electronic conductance speed, the effect of increase storage lithium binding site, can promote lithium ion in charge and discharge process fast
Speed from multiple directions it is embedded, move out, so as to improve the rapid charging performance of negative material, improve cryogenic property and cycle performance, be allowed to
Adaptability of the current electric automobile to lithium ion battery fast charging and discharging and low temperature environment is more adapted to, improves following for lithium ion battery
The ring service life.
Claims (10)
1. a kind of high magnification graphite cathode material, it is characterised in that including graphite kernel and be coated on the hard of graphite core surface
Carbon material layer, the hard carbon material layer is doped with lithium nitride.
2. high magnification graphite cathode material as claimed in claim 1, it is characterised in that the hard carbon material layer also doped with N,
B, S, Cl or F.
3. high magnification graphite cathode material as claimed in claim 1 or 2, it is characterised in that the thickness of the hard carbon material layer
For 100~500nm.
4. a kind of preparation method of high magnification graphite cathode material as claimed in claim 1, it is characterised in that including following step
Suddenly：
1) hard carbon presoma, passivation of lithium powder, graphite are added in nonaqueous solvents and is uniformly mixed, it is spray-dried, prepare presoma
Particle；
2) granular precursor and nitrogen are reacted, prepares nitridation lithium doping presoma, then carry out nitridation lithium doping presoma
Carburizing sintering, to obtain the final product.
5. the preparation method of high magnification graphite cathode material as claimed in claim 4, it is characterised in that described in step 1)
Hard carbon presoma is phenolic resin, one or more combinations in epoxy resin, furfural resin, acrylic resin.
6. the preparation method of high magnification graphite cathode material as described in claim 4 or 5, it is characterised in that in step 1), institute
It is (1~10) to state hard carbon presoma, passivation of lithium powder, the mass ratio of graphite：(0.1~1)：100.
7. the preparation method of high magnification graphite cathode material as claimed in claim 4, it is characterised in that in step 2), first will
Lithium doping presoma and the dopant mixing containing N, B, S, Cl or F element are nitrogenized, then carries out the carburizing sintering.
8. the preparation method of the high magnification graphite cathode material as described in claim 4 or 7, it is characterised in that in step 2), institute
It is granular precursor is reacted with nitrogen using electric spark deposition to state reaction.
9. the preparation method of high magnification graphite cathode material as claimed in claim 8, it is characterised in that in step 2), electrical fire
In flower deposition process, the power that produces electric spark be 600~800W, and voltage is 80~120V, frequency is 500~
1000Hz。
A kind of 10. lithium ion battery of the high magnification graphite cathode material described in usage right requirement 1.
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| CN111224077A (en) * | 2018-11-27 | 2020-06-02 | 中国科学院大连化学物理研究所 | Lithium nitride composite material and preparation and application thereof |
| CN111326721A (en) * | 2018-12-17 | 2020-06-23 | 中信国安盟固利动力科技有限公司 | Preparation method of composite negative electrode pre-embedded lithium material |
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| CN114497451A (en) * | 2022-01-28 | 2022-05-13 | 上海兰钧新能源科技有限公司 | Negative plate and preparation method and application thereof |
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| CN114497451B (en) * | 2022-01-28 | 2024-03-19 | 上海兰钧新能源科技有限公司 | Negative plate and preparation method and application thereof |
| CN114709398A (en) * | 2022-04-17 | 2022-07-05 | 晖阳(贵州)新能源材料有限公司 | Sulfur-containing fast ion conductor coated graphite composite material and preparation method thereof |
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