CN110462890A - Electrode active material, the cathode comprising the electrode active material and battery and the method for preparing the battery - Google Patents
Electrode active material, the cathode comprising the electrode active material and battery and the method for preparing the battery Download PDFInfo
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- CN110462890A CN110462890A CN201780089129.6A CN201780089129A CN110462890A CN 110462890 A CN110462890 A CN 110462890A CN 201780089129 A CN201780089129 A CN 201780089129A CN 110462890 A CN110462890 A CN 110462890A
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M10/04—Construction or manufacture in general
- H01M10/049—Processes for forming or storing electrodes in the battery container
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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
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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
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
Abstract
The present invention relates to the lithium ion battery electrode active materials comprising granular porous silicon or silicon alloy and sodium ion, and wherein sodium ion is embedded in the granular porous silicon or silicon alloy.The invention further relates to the cathode comprising the electrode active material and the lithium ion batteries comprising the cathode.The invention further relates to the methods for preparing lithium ion battery.
Description
Technical field
The present invention relates to the lithium ion battery electrode active material comprising granular porous silicon or silicon alloy and sodium ion,
Wherein sodium ion is embedded in the granular porous silicon or silicon alloy.The invention further relates to negative comprising the electrode active material
Pole and lithium ion battery comprising the cathode.The invention further relates to the methods for preparing lithium ion battery.
Background technique
Silicon is since it is for Li4.4The high theoretical specific capacity of 4200mAh/g for Si, so being a kind of promising optional
Negative electrode material.However, there are two problems to be considered for realizing that its application is critical.One is in charge and discharge process
Volume change, this causes electrode material to rupture and broken, therefore loses the electrical contact and serious appearance between single silicon particle
Amount is reduced.The other is when Si and electrolyte contact superficial layer property, also referred to solid-electrolyte-interface (SEI).
Summary of the invention
Present invention aim to address following problems: the volume change in charge and discharge process, poor Li+Conductibility and difference
Electron conduction.
According on one side, the purpose can by the inclusion of the lithium of granular porous silicon or silicon alloy and sodium ion from
Sub- battery electrode active material realizes that wherein sodium ion is embedded in the granular porous silicon or silicon alloy.
According to another aspect of the present invention, the cathode comprising electrode active material according to the present invention is provided.
According to another aspect of the present invention, the lithium ion battery comprising cathode according to the present invention is provided.
According to another aspect, the purpose can by prepare lithium ion battery method realize, the method includes with
Lower step:
1) positive electrode active materials are provided together with one or more sodium source materials, and granular porous silicon or silicon alloy are provided
As negative electrode active material；
2) by positive electrode active materials 1) together with one or more sodium source materials, 1) negative electrode active material and electrolyte
It is assembled into lithium ion battery；
3) formation process is implemented to lithium ion battery 2).
Detailed description of the invention
Various aspects of the invention are explained in more detail according to attached drawing, in which:
Fig. 1 to 3 is the schematic diagram of the formation process of the method for the present invention；
Fig. 4 show the lithium ion battery of embodiment 1 (E1), embodiment 2 (E2), embodiment 3 (E3) and comparative example (CE)
Cycle performance.
Specific embodiment
All publications addressed herein, patent application, patent and other bibliography herein will if not being otherwise noted
Entire contents are clearly incorporated herein by reference for all purposes, treat as sufficiently illustrating.
Unless otherwise defined, all technical and scientific terms as used herein have with it is of the art common
The identical meaning of the usual understanding of technical staff.In the case of a conflict, this specification of being subject to includes definition.
As range, preferred scope or a series of preferred upper limit values and preferred lower limit value given amounts, concentration or its
When his numerical value or parameter, it should be understood that specifically disclose by any range limit or preferred value and any range lower limit or excellent
Arbitrary all ranges to formation of choosing value, regardless of whether these ranges are disclosed in isolation.If addressing numerical value model herein
It encloses, unless otherwise indicated, which is intended to include its endpoint and all integers and score in the range.
According on one side, the present invention relates to the lithium ion batteries comprising granular porous silicon or silicon alloy and sodium ion
Electrode active material, wherein sodium ion is embedded in the granular porous silicon or silicon alloy.
According to an embodiment of electrode active material according to the present invention, sodium ion can be in the form of sodium-silicon alloy
In the presence of.As shown in Figure 3, sodium ion is no longer taken off by negative electrode material at the end of formation process and in subsequent cyclic process
Out, but formation sodium-silicon alloy in the granular porous silicon or silicon alloy is stayed in.Because the radius of sodium ion be greater than lithium from
Son, so sodium ion can play the effect of the pillar in silicon structure during circulation, to reduce the volume during circulation
It shrinks, and keeps lithiumation/de- lithium channel unimpeded.On the other hand, in subsequent cyclic process, in addition to positive electrode active materials,
The sodium source material can also be deviate from and be embedded in lithium ion, wherein the sodium ion of the sodium source material is partly by lithium ion
Instead of.
According to another embodiment of electrode active material according to the present invention, the weight based on the electrode active material
Amount, the content of sodium ion can be 0.1 to 5 weight %, preferably 0.5 to 2 weight %, more preferably 0.8 to 1.5 weight %.
Because the radius of sodium ion is greater than lithium ion, only small amounts of sodium ion can be embedded in silicon structure.
According to another embodiment of electrode active material according to the present invention, the granular porous silicon or silicon alloy
Average diameter can be 20nm to 20 μm, preferably 0.1 to 10 μm.
According to another embodiment of electrode active material according to the present invention, the granular porous silicon or silicon alloy
BET specific surface area can be 5 to 500m2/g。
According to another embodiment of electrode active material according to the present invention, the granular porous silicon or silicon alloy
Kong Rongke for 0.3 to 50.0cm3/g。
According to another embodiment of electrode active material according to the present invention, the granular porous silicon or silicon alloy
Average pore size can be 0.2nm to 0.1 μm.
The present invention relates to the cathode comprising electrode active material according to the present invention according to another aspect,.
According in another aspect, the present invention relates to the lithium ion batteries comprising cathode according to the present invention.
According to another aspect, the present invention relates to the method for preparing lithium ion battery, the described method comprises the following steps:
1) positive electrode active materials are provided together with one or more sodium source materials, and granular porous silicon or silicon alloy are provided
As negative electrode active material；
2) by positive electrode active materials 1) together with one or more sodium source materials, 1) negative electrode active material and electrolyte
It is assembled into lithium ion battery；
3) formation process is implemented to lithium ion battery 2).
1) positive electrode active materials are provided together with one or more sodium source materials, and granular porous silicon or silicon alloy are provided
As negative electrode active material
In step 1), positive electrode active materials can be provided together with one or more sodium source materials, and can provide
Granular porous silicon or silicon alloy are as negative electrode active material.
According to an embodiment according to the method for the present invention, the sodium source material can be for selected from can be in sodium ion
Positive electrode active materials used in battery it is one or more.Specifically, the sodium source material can be for selected from the following group
One of or it is a variety of:
The binary of sodium and one or more transition metal, ternary or quaternary oxide；
The sulfate of sodium and one or more transition metal；
The ferrocyanide of sodium ferrocyanide and sodium and one or more transition metal；
The phosphate of sodium and one or more transition metal；
The pyrophosphate of sodium pyrophosphate and sodium and one or more transition metal；
The fluorophosphate of sodium fluoro phosphate and sodium and one or more transition metal；And
Organic Sodium Salt,
Wherein one or more transition metal can be in the following group: titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and
Zinc.
According to another embodiment according to the method for the present invention, the sodium source material can be in the following group
It is one or more: sodium phosphate vanadium, sodium phosphate iron, sodium fluoro phosphate vanadium, sodium fluoro phosphate iron and sodium ferrocyanide.
According to another embodiment according to the method for the present invention, the sodium source material can be dehydration.
According to another embodiment according to the method for the present invention, the positive electrode active materials and the sodium source material
Weight ratio can be 12.6:1 to 9:1, preferably 11.6:1 to 10:1, more preferably 11.1:1 to 10.5:1.
2) assembled battery
It, can be by the positive electrode active materials of step 1) together with one or more sodium source materials, step 1) in step 2)
1M LiPF for example in EC:DMC (molar ratio 1:1) of negative electrode active material, diaphragm and electrolyte6It is assembled into lithium-ion electric
Pond.
Specifically, can be by the positive electrode active materials of step 1) together with one or more sodium source materials and carbon black, stone
The adhesive of ink and such as polyvinylidene fluoride (PVDF) mixes in the solvent of such as DMF, TMF, THF or NMP, and is coated in
On aluminium foil, and it is dry.It on the other hand, can be by the negative electrode active material of step 1) and carbon black, graphite and such as Sodium Polyacrylate
Adhesive mixing, and be coated on copper foil, and dry.
3) formation process
Formation process can be implemented to the lithium ion battery of step 2) in step 3).
According to another embodiment according to the method for the present invention, can with C/5 to C/100, preferably C/10 to C/50, more
The current density of preferably from about C/20 implements the formation process.
It, can be by step 2) in the formation process according to another embodiment according to the method for the present invention
Lithium ion battery is charged to 3.7 to 4.0V, preferably 3.8 to 3.9V, even more preferably about 3.85V, is kept for 1 to 10 hour, preferably
It is 4 to 6 hours, is then further charged to charge cutoff voltage.
According to another embodiment according to the method for the present invention, it is possible to implement the formation process until 4.15 to
The charge cutoff voltage of 4.25V, preferably from about 4.2V, and until 2.4 to 2.6V, preferably from about 2.5V discharge cut-off voltage.
According to another embodiment according to the method for the present invention, it is possible to implement the formation process until 4.3 to
The charge cutoff voltage of 4.4V, preferably from about 4.35V, and until 2.9 to 3.1V, preferably from about 3.0V discharge cut-off voltage.
According to another embodiment according to the method for the present invention, in the formation process, sodium ion can be by just
Pole abjection enters in electrolyte (referring to Fig. 1), and is embedded in cathode (referring to fig. 2) by electrolyte.
According to another embodiment according to the method for the present invention, in the formation process, sodium ion can be embedded in
Sodium-silicon alloy is formed in the granular porous silicon or silicon alloy of negative electrode active material.As shown in Figure 3, sodium ion had been melted into
No longer deviate from by negative electrode material at the end of journey and in subsequent cyclic process, but stays in the granular porous silicon or silicon conjunction
Sodium-silicon alloy is formed in gold.Because the radius of sodium ion is greater than lithium ion, sodium ion can play silicon knot during circulation
The effect of pillar in structure to reduce the volume contraction during circulation, and keeps lithiumation/de- lithium channel unimpeded.It is another
Aspect, in subsequent cyclic process, in addition to positive electrode active materials, sodium source material can also be deviate from and be embedded in lithium ion
Material, wherein the sodium ion of the sodium source material is partly replaced by lithium ion.
4) it is replaced with fresh electrolyte
According to another embodiment according to the method for the present invention, the method can also optionally wrap after step 3)
Include step 4), in step 4) electrolyte can with same composition fresh electrolyte for example EC:DMC (molar ratio 1:
1) the 1M LiPF in6It is replaced, thus the electrolyte in battery substantially no longer includes sodium ion, as shown in Figure 3.
According to the present invention, sodium may be used to silicium cathode activation.The sodium source material can be initially introduced into anode.
During initial chemical conversion circulation, sodium ion can be deviate from by anode structure, and diffuse to negative side by side of the positive electrode.Then, electric
The lithium and sodium ion of Xie Zhizhong can be embedded in silicium cathode.
Because the radius of sodium ion is greater than lithium ion, sodium ion can play the effect of the pillar in silicon structure, from
And reduce the volume change in charge and discharge process.It is thereby achieved that better cycle performance and better high rate performance.
Specifically, can solve following problems through the invention:
1) volume change in charge and discharge process:
When in some sodium ions insertion silicon structure, the volume of silicon structure can expand, but will not shrink, thus can subtract
Small size variation；
2) poor Li+Conductibility:
Because in some sodium ion insertion silicon structures the diffusion admittance of lithium ion can be expanded, so as to improve Li+Conduction
Property；
3) poor electron conduction:
Continuous volume change causes to lose the electrical contact between silicon particle, however according to the present invention it is possible to reduces volume
Variation, and more preferably electron conduction may be implemented.
Embodiment 1 (E1):
Preparation anode:
Use Na4Fe(CN)6·xH2O stays overnight dehydration as sodium source material, obtains Na4Fe(CN)6.Then ball is utilized
Grinding machine is with the rate of 200rpm by Na4Fe(CN)6With conductive black Super P (can be commercially available by Timcal) with the weight of 8:2
Than mixing 2 hours, ready-mixed object is obtained.
Weigh up 10 grams of ready-mixed objects, 86.5 grams of NCM111 (can be commercially available by BASF), 2 grams of PVDF (can be by Solef quotient
Purchase obtains), 1 gram of conductive black Super P (can be commercially available by Timcal) and 0.5 gram of flake graphite be (commercially available from can be by Timcal
Obtain), it is then dry-mixed, obtain intermediate blend.
Intermediate blend is added to nmp solvent, anode sizing agent is obtained, wherein the solid content of anode sizing agent is adjusted to
About 68 weight %.Anode sizing agent is coated on aluminium foil, and dry at about 80 DEG C, to obtain anode.
Prepare cathode:
Using the 40 granular porous silicon alloys of weight % (can be commercially available by 3M), 40 weight % graphite (commercially available from can be by BTR
Obtain), 10 weight % Sodium Polyacrylates (NaPAA), 8 weight % flake graphites (can be commercially available by Timcal) and 2 weight %
Conductive black Super P (can be commercially available by Timcal) prepares cathode composition.Cathode composition is coated on copper foil, and
It is dried, to obtain cathode.
Assembled battery:
Use the 1M LiPF in dimethyl carbonate (DMC) and ethylene carbonate (EC) (molar ratio 1:1)6As electrolysis
Matter.Use PI film (can be commercially available by DuPont) as diaphragm.
Anode, cathode, electrolyte and diaphragm are assembled into the glove box (MB-10compact, MBraun) of applying argon gas
Soft-package battery.
Formation process and subsequent cyclic process:
Chemical property is assessed at room temperature on LAND-CT 2001A type battery test system (Wuhan, China).
Formation process is implemented to soft-package battery, wherein soft-package battery charges to 3.85V with the current density of C/20, keeps 5
Hour, 4.2V is further charged to, and be discharged to 2.5V.Soft-package battery is in subsequent cyclic process with the current density of 0.5C
It charges to 4.2V and is discharged to 2.5V.
Fig. 4 show the cycle performance of the lithium ion battery of embodiment 1 (E1).
Embodiment 2 (E2):
Embodiment 2 (E2) is implemented similar to Example 1ly, and difference is, soft-package battery is every in subsequent cyclic process
50 times circulation is charged and discharged with the current density of 0.1C, and other circulations are then filled with the current density of 0.5C
Electricity and electric discharge.
Fig. 4 show the cycle performance of the lithium ion battery of embodiment 2 (E2).
Embodiment 3 (E3):
Embodiment 3 (E3) is implemented similar to Example 1ly, and difference is, soft-package battery is in formation process with C/20's
Current density charges to 3.85V, is kept for 5 hours, further charges to 4.35V, and be discharged to 3V；And in subsequent cyclic process
Middle every 50 circulations of soft-package battery are then charged to other circulations with the current density of 0.1C with the current density of 0.5C
4.35V and it is discharged to 3V.
Fig. 4 show the cycle performance of the lithium ion battery of embodiment 3 (E3).
Comparative example (CE):
Comparative example (CE) is implemented similar to Example 1ly, and difference is, without using sodium source material preparation anode.
Fig. 4 show the cycle performance of the lithium ion battery of comparative example (CE).
The potential application of electrode active material according to the present invention includes but is not limited to have for such as electric tool, light
Lie prostrate the lithium ion battery of the high-energy density of the acceptable high power density of stored energy application of battery and electric vehicle.
Although describing certain embodiments, these embodiments are only to present in an exemplary fashion, should not be limited
The scope of the present invention.Appended claims and its equivalent should cover fall within the spirit and scope of the invention it is all
Modification, substitution and change scheme.
Claims (23)
1. being used for the electrode active material of lithium ion battery, which is characterized in that the electrode active material includes granular porous
Silicon or silicon alloy and sodium ion, wherein sodium ion is embedded in the granular porous silicon or silicon alloy.
2. electrode active material according to claim 1, which is characterized in that sodium ion exists in the form of sodium-silicon alloy.
3. electrode active material according to claim 1 or 2, which is characterized in that the weight based on the electrode active material, sodium
The content of ion is 0.1 to 5 weight %, preferably 0.5 to 2 weight %, more preferably 0.8 to 1.5 weight %.
4. according to claim 1 to one of 3 electrode active material, which is characterized in that the granular porous silicon or silicon alloy
Average diameter be 20nm to 20 μm, preferably 0.1 to 10 μm.
5. according to claim 1 to one of 4 electrode active material, which is characterized in that the granular porous silicon or silicon alloy
BET specific surface area be 5 to 500m2/g。
6. according to claim 1 to one of 5 electrode active material, which is characterized in that the granular porous silicon or silicon alloy
Kong Rongwei 0.3 to 50.0cm3/g。
7. according to claim 1 to one of 6 electrode active material, which is characterized in that the granular porous silicon or silicon alloy
Average pore size be 0.2nm to 0.1 μm.
8. be used for lithium ion battery cathode, which is characterized in that the cathode include according to claim 1 to one of 7 electrode
Active material.
9. lithium ion battery, which is characterized in that the lithium ion battery includes cathode according to claim 8.
10. the method for preparing lithium ion battery, the described method comprises the following steps:
1) positive electrode active materials are provided together with one or more sodium source materials, and granular porous silicon or silicon alloy conduct are provided
Negative electrode active material；
2) 1) positive electrode active materials are assembled together with one or more sodium source materials, 1) negative electrode active material and electrolyte
At lithium ion battery；
3) formation process is implemented to lithium ion battery 2).
11. method according to claim 10, which is characterized in that the sodium source material is selected from can make in sodium-ion battery
Positive electrode active materials it is one or more.
12. 0 or 11 method according to claim 1, which is characterized in that the sodium source material is selected from one of the following group
Or it is a variety of:
The binary of sodium and one or more transition metal, ternary or quaternary oxide；
The sulfate of sodium and one or more transition metal；
The ferrocyanide of sodium ferrocyanide and sodium and one or more transition metal；
The phosphate of sodium and one or more transition metal；
The pyrophosphate of sodium pyrophosphate and sodium and one or more transition metal；
The fluorophosphate of sodium fluoro phosphate and sodium and one or more transition metal；And
Organic Sodium Salt.
13. method according to claim 12, which is characterized in that one or more transition metal are in the following group: titanium,
Vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc.
14. one of 0 to 13 method according to claim 1, which is characterized in that the sodium source material is in the following group
It is one or more: sodium phosphate vanadium, sodium phosphate iron, sodium fluoro phosphate vanadium, sodium fluoro phosphate iron and sodium ferrocyanide.
15. one of 0 to 14 method according to claim 1, which is characterized in that the sodium source material is dehydration.
16. one of 0 to 15 method according to claim 1, which is characterized in that the positive electrode active materials and sodium source material
The weight ratio of material is 12.6:1 to 9:1, preferably 11.6:1 to 10:1, more preferably 11.1:1 to 10.5:1.
17. one of 0 to 16 method according to claim 1, which is characterized in that with C/5 to C/100, preferably C/10 to C/50, more
The current density of preferably from about C/20 implements the formation process.
18. one of 0 to 16 method according to claim 1, which is characterized in that in the formation process, by lithium ion 2)
Battery is charged to 3.7 to 4.0V, preferably 3.8 to 3.9V, even more preferably about 3.85V, is kept for 1 to 10 hour, and preferably 4 to 6
Hour, then further it is charged to charge cutoff voltage.
19. one of 0 to 18 method according to claim 1, which is characterized in that implement the formation process until 4.15 to
The charge cutoff voltage of 4.25V, preferably from about 4.2V, and until 2.4 to 2.6V, preferably from about 2.5V discharge cut-off voltage.
20. one of 0 to 19 method according to claim 1, which is characterized in that implement the formation process until 4.3 to 4.4V,
The preferably from about charge cutoff voltage of 4.35V, and until 2.9 to 3.1V, preferably from about 3.0V discharge cut-off voltage.
21. one of 0 to 20 method according to claim 1, which is characterized in that in the formation process, sodium ion is by anode
Abjection enters in electrolyte, and by electrolyte insertion cathode.
22. method according to claim 21, which is characterized in that in the formation process, it is living that sodium ion is embedded in the cathode
Property material granular porous silicon or silicon alloy in formed sodium-silicon alloy.
23. one of 0 to 22 method according to claim 1, which is characterized in that after step 3), the electrolyte is with having
The fresh electrolyte of same composition is replaced.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2017/078550 WO2018176254A1 (en) | 2017-03-29 | 2017-03-29 | Electrode active material, an anode and a battery containing said electrode active material, and a method for preparing a battery |
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| CN110462890A true CN110462890A (en) | 2019-11-15 |
| CN110462890B CN110462890B (en) | 2022-08-16 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114551880A (en) * | 2021-12-21 | 2022-05-27 | 杭州华宏通信设备有限公司 | Carbon-coated porous Cr-Cu alloy/lithium iron phosphate positive electrode and preparation method thereof |
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| CN103165874A (en) * | 2013-04-10 | 2013-06-19 | 上海空间电源研究所 | Porous silicon negative material of lithium ion battery and preparation method and application of material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114551880A (en) * | 2021-12-21 | 2022-05-27 | 杭州华宏通信设备有限公司 | Carbon-coated porous Cr-Cu alloy/lithium iron phosphate positive electrode and preparation method thereof |
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| WO2018176254A1 (en) | 2018-10-04 |
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