CN109585813A - A kind of lithium sulfur battery anode material and preparation method of graphene coated - Google Patents
A kind of lithium sulfur battery anode material and preparation method of graphene coated Download PDFInfo
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- CN109585813A CN109585813A CN201811358183.9A CN201811358183A CN109585813A CN 109585813 A CN109585813 A CN 109585813A CN 201811358183 A CN201811358183 A CN 201811358183A CN 109585813 A CN109585813 A CN 109585813A
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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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of lithium sulfur battery anode material of graphene coated and preparation methods.The lithium sulfur battery anode material is made by following steps: lithium metal powder, silicon carbide powder uniformly a, being mixed to get mixed-powder；B, it after by mixed-powder using hydrogen etching, is then passed through argon gas and carbon disulfide gas is heat-treated, obtain positive electrode particle；C, by positive electrode particle compression moulding, the lithium sulfur battery anode material of graphene coated is made.The method has the advantages that positive electrode prepared by the present invention without additional addition conductive agent, it is high that it carries sulfur content, compactness is good, the current-carrying capacity due to caused by addition a large amount of conductive agents is low during solving the problems, such as conventional synthesis, when in use, only there is volume contraction in lithium sulfide lithium de- first during deintercalation, the graphene layer of external sheath will not be caused to rupture, to improve the cycle performance of battery.
Description
Technical field
The present invention relates to lithium-sulfur cell fields, and in particular to the preparation of lithium sulfur battery anode material, more particularly, to one kind
The lithium sulfur battery anode material and preparation method of graphene coated.
Background technique
There is an urgent need to develop the batteries of higher energy density for the rapid development of new-energy automobile and mobile electronic device.New
Energy storage system in, using lithium metal as cathode, elemental sulfur or sulfur-based compound be anode lithium-sulfur cell theoretical specific energy it is remote
Secondary cell is commercialized higher than used at this stage.In addition, cheap, the environmental-friendly characteristic of elemental sulfur makes the system great again
Commercial value.Lithium-sulfur cell has high energy density, is the existing preferred option for solving lithium ion battery energy throughput bottleneck.Cause
This, lithium-sulfur cell is acknowledged as next-generation most potential high-energy-density secondary cell system.
Lithium sulfur battery anode material is divided into carbon/sulphur composite material, nano metal chemical combination object/sulphur composite material, polymer/sulphur
3 major class of composite material.Defect of sulphur itself be influence lithium-sulfur cell performance important bottleneck, the poorly conductive of sulfur-based compound,
It needs to add a large amount of conductive additive, is affected for the mass energy density of battery.In addition, more vulcanizations of lithium-sulfur cell
The shuttle effect and sulphur anode volume of lithium change greatly, and influence the unfavorable factor of the cycle performance of battery.Thus by just
The study on the modification of pole material solves the above problem of lithium-sulfur cell, is the main path for improving battery performance.
Number of patent application 201711259805.8 discloses a kind of lithium sulfur battery anode material, mainly by sheet N doping
Carbon fiber is placed on above the sheet form base for being deposited with nano-sulfur particles obtained by lamination, wherein is deposited with the piece of nano-sulfur particles
Shape substrate is made as follows: being 1 ~ 5L/min's with flow velocity after sulphur powder heating stirring to 120 ~ 300 DEG C of generation sulfur vapors
Nitrogen or argon gas purge sulfur vapor on sheet form base surface.
Number of patent application 201810005304.5 discloses a kind of lithium sulfur battery anode material preparation method, preparation method packet
It includes: preparing sulphur carbon composite；Conductive metal is loaded in sulphur carbon-carbon composite material surface, it is multiple to obtain conductive metal, sulphur and carbon material
The composite material of conjunction.The method of the invention has been able to suppress " the shuttle effect " and positive electrode volume expansion of polysulfide
Effect effectively improves the cycle performance of battery.
Number of patent application 201310428298.1 discloses a kind of sulphur for lithium-sulfur cell/porous carbon enveloped carbon nanometer tube
Composite positive pole and preparation method thereof, the lithium-sulfur battery composite cathode material are received by the porous carbon carbon coated with micro-nano structure
Mitron complex carbon material is combined with elemental sulfur；Preparation method is poly- Abbado amine to be first wrapped in carbon nano tube surface, then lead to
Cross after high temperature carbonization and elemental sulfur it is compound to get；The preparation method is easy to operate, at low cost, and lithium-sulfur cell obtained is compound just
Pole material utilization efficiency is high, substantially increases the cycle performance of lithium-sulfur cell.
Number of patent application 201711366786.9 discloses a kind of lithium sulfur battery anode material and preparation method thereof, the lithium sulphur
Cell positive material is the redox graphene aeroge nesting sulphur nano particle composite material with tridimensional network.It should
The preparation method of lithium sulfur battery anode material, be formed by online redox graphene colloidal sol and sulphur collosol intermixture it is solidifying
Glue, then freeze-drying obtains the redox graphene aeroge nesting sulphur nano-particles reinforcement material with tridimensional network
Material；It specifically uses graphene oxide as starting material, prepares the mixed sols of graphene oxide and sulphur, it is online at room temperature to go back
Original method prepares redox graphene gel cladding sulphur nano particle composite material, removes internal cladding by freeze-drying
Solvent obtains redox graphene aeroge nesting sulphur nano particle composite material.
It can be seen that the prior art improves in the technical method of lithium sulfur battery anode material, generally existing effect is undesirable
Defect, especially sulphur is penetrated into the conductive material of nano-porous structure, improves electronic conductivity and ionic conductivity
Method, due in nano-porous structure since there are a large amount of holes, it is difficult to effectively inhibit more lithium sulfides dissolution and improve anode
The load sulfur content of material, while utilization during sulfur-based positive electrode dilation for hole is difficult to realize effective circular form
And stability.Therefore for the optimization of the improvement of lithium sulfur battery anode material and technique, to improve, it carries sulfur content and inhibition volume is swollen
It is swollen that there is highly important practical significance.
Summary of the invention
Effectively to solve above-mentioned technical problem, the invention proposes a kind of lithium sulfur battery anode material of graphene coated and
Preparation method, can effectively improve the load sulfur content of positive electrode, and solve the problems, such as positive electrode volume expansion.
The specific technical solution of the present invention is as follows:
A kind of preparation method of the lithium sulfur battery anode material of graphene coated: the lithium sulfur battery anode material is lithium metal
After powder is mixed with silicon carbide, hydrogen etching is carried out, is then heat-treated under argon gas and carbon disulfide gas, forms lithium sulfide
Simultaneously in surface layer coated graphite alkene layer, compression moulding and be made, specific preparation step are as follows:
A, ball mill is added in lithium metal powder, silicon carbide powder, uniformly mixes, obtains mixed-powder；
B, mixed-powder made from step a is added in vacuum drying oven, after etching using hydrogen, is then passed through argon gas and carbon disulfide
Gas is heat-treated, later heating and held for some time, and reaction forms a small amount of graphene of lithium sulfide and surface layer cladding, stone
Clad is collectively formed in black alkene and silicon carbide, obtains the positive electrode particle of graphene uniform cladding lithium sulfide；
C, by the positive electrode particle compression moulding of the cladding lithium sulfide of graphene uniform made from step b, graphene coated is made
Lithium sulfur battery anode material.
Preferably, in the step a, ball mill can be one in tube mill, bar type ball mill, horizontal ball mill
Kind.
Preferably, in step a, 94 ~ 97 parts by weight of lithium metal powder, 3 ~ 6 parts by weight of silicon carbide powder.
Preferably, in the step b, vacuum drying oven can be vacuum resistance furnace, vaccum sensitive stove, vacuum arc furnace ignition, vacuum electric
One of beamlet furnace, vacuum plasma furnace.
Preferably, in the step b, the temperature of hydrogen etching is 700 ~ 800 DEG C, and pressure is normal pressure, the time is 30 ~
40min。
Preferably, in the step b, argon gas, carbon disulfide volume ratio be 1:0.5 ~ 1.
Preferably, in the step b, the temperature of heat treatment is 650 ~ 750 DEG C, and the time is 60 ~ 90min.
Preferably, in the step b, the temperature after heating is 1300 ~ 1400 DEG C, and soaking time is 80 ~ 100min.
Preferably, in the step c, the pressure of compression moulding is 1 ~ 2MPa, and the dwell time is 8 ~ 12s.
The present invention reacted under heat treatment with carbon disulfide gas by lithium metal to be formed lithium sulfide and surface layer cladding lack
Graphene is measured, after clad is collectively formed in graphene and the silicon carbide for exposing active surface after hydrogen etches, after heating
Heat preservation heat treatment makes silicon atom distil, and remaining carbon-based material is epitaxially-formed uniform clad along graphene layer, obtains stone
Black alkene uniformly coats the positive electrode particle of lithium sulfide, significantly improves the load sulfur content of positive electrode, and be not in volume
Expansion.
Above content of the present invention also proposes a kind of lithium sulfur battery anode material of graphene coated, is made by following steps:
A, lithium metal powder, silicon carbide powder are uniformly mixed to get mixed-powder；B, after by mixed-powder using hydrogen etching, then
It is passed through argon gas and carbon disulfide gas is heat-treated, obtain positive electrode particle；C, by positive electrode particle compression moulding, i.e.,
?.
The invention has the benefit that
1. proposing graphene and silicon carbide forming the method that clad prepares the lithium sulfur battery anode material of graphene coated.
2. positive electrode prepared by the present invention without additional addition conductive agent, carries, sulfur content is high, and compactness is good, solves biography
Integration is in the process due to adding the problem that load sulfur content is low caused by a large amount of conductive agents.
3. positive electrode prepared by the present invention is when in use, only there is volume in lithium sulfide lithium de- first during deintercalation
It shrinks, the graphene layer of external sheath will not be caused to rupture, to improve the cycle performance of battery.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A, tube mill is added in lithium metal powder, silicon carbide powder, uniformly mixes, obtains mixed-powder；Wherein, lithium metal
95 parts by weight of powder, 5 parts by weight of silicon carbide powder；
B, mixed-powder made from step a is added in vacuum drying oven resistance, after being etched using hydrogen, the temperature of hydrogen etching is
750 DEG C, pressure is normal pressure, and time 35min, is then passed through argon gas and carbon disulfide gas is heat-treated, argon gas, curing
The volume ratio of carbon is 1:0.8, and the temperature of heat treatment is 700 DEG C, time 75min, later heating and held for some time, heating
Temperature afterwards is 1350 DEG C, soaking time 90min, and reaction forms a small amount of graphene of lithium sulfide and surface layer cladding, graphene
Clad is collectively formed with silicon carbide, obtains the positive electrode particle of graphene uniform cladding lithium sulfide；
C, by the positive electrode particle compression moulding of the cladding lithium sulfide of graphene uniform made from step b, the pressure of compression moulding
For 1.5MPa, dwell time 10s, the lithium sulfur battery anode material of graphene coated is made.
Embodiment 2
A, bar type ball mill is added in lithium metal powder, silicon carbide powder, uniformly mixes, obtains mixed-powder；Wherein, lithium metal
94 parts by weight of powder, 6 parts by weight of silicon carbide powder；
B, mixed-powder made from step a is added in vacuum drying oven induction, after being etched using hydrogen, the temperature of hydrogen etching is
700 DEG C, pressure is normal pressure, and time 40min, is then passed through argon gas and carbon disulfide gas is heat-treated, argon gas, curing
The volume ratio of carbon is 1:0.5, and the temperature of heat treatment is 650 DEG C, time 90min, later heating and held for some time, heating
Temperature afterwards be 1300 ~ DEG C, soaking time 100min, reaction formed lithium sulfide and surface layer cladding a small amount of graphene, graphite
Clad is collectively formed in alkene and silicon carbide, obtains the positive electrode particle of graphene uniform cladding lithium sulfide；
C, by the positive electrode particle compression moulding of the cladding lithium sulfide of graphene uniform made from step b, the pressure of compression moulding
For 1MPa, dwell time 12s, the lithium sulfur battery anode material of graphene coated is made.
Embodiment 3
A, horizontal ball mill is added in lithium metal powder, silicon carbide powder, uniformly mixes, obtains mixed-powder；Wherein, lithium metal
97 parts by weight of powder, 3 parts by weight of silicon carbide powder；
B, mixed-powder made from step a is added in vacuum arc furnace ignition, after being etched using hydrogen, the temperature of hydrogen etching is
800 DEG C, pressure is normal pressure, and time 30min, is then passed through argon gas and carbon disulfide gas is heat-treated, argon gas, curing
The volume ratio of carbon is 1:1, and the temperature of heat treatment is 750 DEG C, time 60min, later heating and held for some time, heating
Temperature afterwards is 1400 DEG C, soaking time 80min, and reaction forms a small amount of graphene of lithium sulfide and surface layer cladding, graphene
Clad is collectively formed with silicon carbide, obtains the positive electrode particle of graphene uniform cladding lithium sulfide；
C, by the positive electrode particle compression moulding of the cladding lithium sulfide of graphene uniform made from step b, the pressure of compression moulding
For 2MPa, dwell time 8s, the lithium sulfur battery anode material of graphene coated is made.
Embodiment 4
A, tube mill is added in lithium metal powder, silicon carbide powder, uniformly mixes, obtains mixed-powder；Wherein, lithium metal
95 parts by weight of powder, 5 parts by weight of silicon carbide powder；
B, mixed-powder made from step a is added in vacuum electron beam furnace, after being etched using hydrogen, the temperature of hydrogen etching is
720 DEG C, pressure is normal pressure, and time 38min, is then passed through argon gas and carbon disulfide gas is heat-treated, argon gas, curing
The volume ratio of carbon is 1:0.6, and the temperature of heat treatment is 680 DEG C, time 80min, later heating and held for some time, heating
Temperature afterwards is 1330 DEG C, soaking time 95min, and reaction forms a small amount of graphene of lithium sulfide and surface layer cladding, graphene
Clad is collectively formed with silicon carbide, obtains the positive electrode particle of graphene uniform cladding lithium sulfide；
C, by the positive electrode particle compression moulding of the cladding lithium sulfide of graphene uniform made from step b, the pressure of compression moulding
For 1MPa, dwell time 11s, the lithium sulfur battery anode material of graphene coated is made.
Embodiment 5
A, horizontal ball mill is added in lithium metal powder, silicon carbide powder, uniformly mixes, obtains mixed-powder；Wherein, lithium metal
96 parts by weight of powder, 4 parts by weight of silicon carbide powder；
B, mixed-powder made from step a is added in vacuum plasma furnace, after being etched using hydrogen, the temperature of hydrogen etching is
780 DEG C, pressure is normal pressure, and time 33min, is then passed through argon gas and carbon disulfide gas is heat-treated, argon gas, curing
The volume ratio of carbon is 1:0.9, and the temperature of heat treatment is 720 DEG C, time 70min, later heating and held for some time, heating
Temperature afterwards is 1380 DEG C, soaking time 85min, and reaction forms a small amount of graphene of lithium sulfide and surface layer cladding, graphene
Clad is collectively formed with silicon carbide, obtains the positive electrode particle of graphene uniform cladding lithium sulfide；
C, by the positive electrode particle compression moulding of the cladding lithium sulfide of graphene uniform made from step b, the pressure of compression moulding
For 2MPa, dwell time 9s, the lithium sulfur battery anode material of graphene coated is made.
Comparative example 1
A, tube mill is added in lithium metal powder, silicon carbide powder, uniformly mixes, obtains mixed-powder；Wherein, lithium metal
95 parts by weight of powder, 5 parts by weight of silicon carbide powder；
B, mixed-powder made from step a is added in vacuum resistance furnace, is passed through argon gas and carbon disulfide gas is heat-treated,
Argon gas, carbon disulfide volume ratio be 1:0.8, the temperature of heat treatment is 700 DEG C, and time 75min obtains positive electrode
Grain；
C, by positive electrode particle compression moulding made from step b, the pressure of compression moulding is 1.5MPa, dwell time 10s,
The lithium sulfur battery anode material of graphene coated is made.
1 volume change of above-described embodiment 1 ~ 5 and comparative example: positive electrode produced by the present invention is taken, volume is accurately weighed
V, then as anode, using lithium piece as cathode, electrolyte LiTFSI/DOL-DMC(1:1), in the glove box for being full of argon gas
In be assembled into battery sample, carry out charge-discharge test after standing 5h, charge and discharge cycles test carried out by multiplying power with 1C, is tested respectively
Anode volume V at 50 times, 100 times and 200 timesi, volume change: B=(V-V is calculated according to formulai)/V × 100%.
The results are shown in Table 1.
Table 1:
Claims (10)
1. a kind of preparation method of the lithium sulfur battery anode material of graphene coated, it is characterised in that: the lithium-sulphur cell positive electrode
Material is to carry out hydrogen etching after lithium metal powder is mixed with silicon carbide, be then heat-treated under argon gas and carbon disulfide gas,
Formed lithium sulfide while in surface layer coated graphite alkene layer, compression moulding and be made, specific preparation step are as follows:
A, ball mill is added in lithium metal powder, silicon carbide powder, uniformly mixes, obtains mixed-powder；
B, mixed-powder made from step a is added in vacuum drying oven, after etching using hydrogen, is then passed through argon gas and carbon disulfide
Gas is heat-treated, later heating and held for some time, and reaction forms a small amount of graphene of lithium sulfide and surface layer cladding, stone
Clad is collectively formed in black alkene and silicon carbide, obtains the positive electrode particle of graphene uniform cladding lithium sulfide；
C, by the positive electrode particle compression moulding of the cladding lithium sulfide of graphene uniform made from step b, graphene coated is made
Lithium sulfur battery anode material.
2. a kind of preparation method of the lithium sulfur battery anode material of graphene coated according to claim 1, it is characterised in that:
In the step a, ball mill is one of tube mill, bar type ball mill, horizontal ball mill.
3. a kind of preparation method of the lithium sulfur battery anode material of graphene coated according to claim 1, it is characterised in that:
In step a, 94 ~ 97 parts by weight of lithium metal powder, 3 ~ 6 parts by weight of silicon carbide powder.
4. a kind of preparation method of the lithium sulfur battery anode material of graphene coated according to claim 1, it is characterised in that:
In the step b, vacuum drying oven is vacuum resistance furnace, vaccum sensitive stove, vacuum arc furnace ignition, vacuum electron beam furnace, vacuum plasma
One of furnace.
5. a kind of preparation method of the lithium sulfur battery anode material of graphene coated according to claim 1, it is characterised in that:
In the step b, the temperature of hydrogen etching is 700 ~ 800 DEG C, and pressure is normal pressure, and the time is 30 ~ 40min.
6. a kind of preparation method of the lithium sulfur battery anode material of graphene coated according to claim 1, it is characterised in that:
In the step b, argon gas, carbon disulfide volume ratio be 1:0.5 ~ 1.
7. a kind of preparation method of the lithium sulfur battery anode material of graphene coated according to claim 1, it is characterised in that:
In the step b, the temperature of heat treatment is 650 ~ 750 DEG C, and the time is 60 ~ 90min.
8. a kind of preparation method of the lithium sulfur battery anode material of graphene coated according to claim 1, it is characterised in that:
In the step b, the temperature after heating is 1300 ~ 1400 DEG C, and soaking time is 80 ~ 100min.
9. a kind of preparation method of the lithium sulfur battery anode material of graphene coated according to claim 1, it is characterised in that:
In the step c, the pressure of compression moulding is 1 ~ 2MPa, and the dwell time is 8 ~ 12s.
10. a kind of lithium sulfur battery anode material for graphene coated that any one of claim 1 ~ 9 the method is prepared.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112125322A (en) * | 2020-08-03 | 2020-12-25 | 浙江工业大学 | Green and efficient preparation method of lithium sulfide |
| CN112467123A (en) * | 2020-08-14 | 2021-03-09 | 珠海中科兆盈丰新材料科技有限公司 | High-capacity lithium ion battery cathode material and preparation method thereof |
| CN113839045A (en) * | 2021-11-30 | 2021-12-24 | 北京石墨烯技术研究院有限公司 | Graphene/lithium composite material and preparation method and application thereof |
| CN114132970A (en) * | 2021-11-25 | 2022-03-04 | 蜂巢能源科技有限公司 | Method for improving cycle stability of positive electrode material, positive electrode material and lithium ion battery |
| WO2023006000A1 (en) * | 2021-07-30 | 2023-02-02 | 深圳市德方创域新能源科技有限公司 | Core-shell positive electrode lithium-supplementing additive, preparation method therefor and application thereof |
| CN115986112A (en) * | 2023-03-21 | 2023-04-18 | 成都顿威新型金属材料有限公司 | Preparation method and application of lithium sulfide |
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2018
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112125322A (en) * | 2020-08-03 | 2020-12-25 | 浙江工业大学 | Green and efficient preparation method of lithium sulfide |
| CN112125322B (en) * | 2020-08-03 | 2022-04-15 | 浙江工业大学 | Green and efficient preparation method of lithium sulfide |
| CN112467123A (en) * | 2020-08-14 | 2021-03-09 | 珠海中科兆盈丰新材料科技有限公司 | High-capacity lithium ion battery cathode material and preparation method thereof |
| WO2023006000A1 (en) * | 2021-07-30 | 2023-02-02 | 深圳市德方创域新能源科技有限公司 | Core-shell positive electrode lithium-supplementing additive, preparation method therefor and application thereof |
| CN114132970A (en) * | 2021-11-25 | 2022-03-04 | 蜂巢能源科技有限公司 | Method for improving cycle stability of positive electrode material, positive electrode material and lithium ion battery |
| CN114132970B (en) * | 2021-11-25 | 2023-12-29 | 蜂巢能源科技有限公司 | Method for improving circulation stability of positive electrode material, positive electrode material and lithium ion battery |
| CN113839045A (en) * | 2021-11-30 | 2021-12-24 | 北京石墨烯技术研究院有限公司 | Graphene/lithium composite material and preparation method and application thereof |
| CN115986112A (en) * | 2023-03-21 | 2023-04-18 | 成都顿威新型金属材料有限公司 | Preparation method and application of lithium sulfide |
| CN115986112B (en) * | 2023-03-21 | 2023-06-13 | 成都顿威新型金属材料有限公司 | Preparation method and application of lithium sulfide |
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