CN114242989B - Composite electrode material and preparation method and application thereof - Google Patents
Composite electrode material and preparation method and application thereof Download PDFInfo
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
Abstract
The invention provides a composite electrode material and a preparation method and application thereof, the composite electrode material comprises a pole piece substrate and an artificial solid electrolyte layer coated on the surface of the pole piece substrate, the artificial solid electrolyte layer is composed of a first polymer, and the structure of the first polymer is shown as formula I:
(formula I); wherein n = 10-1000; the pole piece substrate is at least one of lithium metal or a composite material containing metal lithium. According to the invention, the ether side group-containing copolymer is coated on the surface of the electrode substrate as the artificial solid electrolyte layer to protect the electrode substrate, the interface of the solid electrolyte layer has high ion conductivity and strong lithium affinity, lithium ions are induced to be uniformly deposited while the electrolyte is prevented from reacting with the electrode substrate, the interface of the electrode substrate is stabilized, and further the consumption of the electrolyte is reduced.
Description
Technical Field
The invention relates to the field of composite electrode preparation, in particular to a composite electrode material and a preparation method and application thereof.
Background
With the rapid development of society, the demand of electric vehicles and consumer electronics is increasing, and the search for new energy materials to replace the original petrochemical materials becomes an important subject for the development of new era. The lithium metal as the battery cathode material can provide extremely high specific capacity (3860 mAh/g) and a larger working voltage window (the reduction electrode potential is-3.04V), and is an effective next-generation new energy material. However, the high activity, large volume deformation and lithium dendrite problems of the metallic lithium itself have been obstacles limiting the application of metallic lithium negative electrodes. At present, the main problems of the lithium metal as the negative electrode of the lithium battery are as follows: (1) the volume deformation of the metal lithium is very large in the charging and discharging processes, so that the battery has large expansion and contraction; (2) lithium metal tends to grow lithium dendrites during deposition due to kinetic and thermodynamic reasons, which not only forms dead lithium to reduce the negative electrode capacity and increase the polarization of the battery, but also may cause internal short circuits to cause battery failure and even fire explosion. In addition, the low reduction potential of lithium makes it unstable in conventional electrolytes, resulting in reduction of the electrolyte at the lithium metal surface, forming a passivation layer (this passivation layer is commonly referred to as "solid electrolyte interface layer (SEI)"). Defects and cracks in the SEI can lead to local lithium ion enrichment and dendrite growth, while increasing the surface area of the lithium negative electrode, leading to irreversible consumption of active lithium, forming a new SEI on its surface. The vicious circle of the two behaviors causes the continuous reduction of the battery capacity and the low coulombic efficiency, and the application and the development of the lithium battery are seriously hindered.
Therefore, the dynamic stability of the SEI is crucial to obtain excellent energy storage performance and long cycle life. Currently, there are few reports on the achievement of energy storage performance and cycle stability life by maintaining the dynamic stability of SEI.
Disclosure of Invention
In view of the above technical problems in the prior art, it is an object of the present invention to provide a composite electrode material, which is prepared by coating an ether-containing side group copolymer as an artificial solid electrolyte layer on the surface of an electrode substrate to protect the electrode substrate. The solid electrolyte layer interface has high ion conduction rate and strong lithium affinity, induces uniform deposition of lithium ions, prevents the electrolyte from reacting with an electrode matrix, stabilizes the electrode matrix interface and further reduces the consumption of electrolyte.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the utility model provides a composite electrode material, includes the pole piece base member and the cladding is in the artifical solid electrolyte layer of pole piece base member surface, artifical solid electrolyte layer comprises first polymer, first polymer structure is shown as formula I:
In some embodiments, the first polymer is prepared by reacting a second polymer having a structure according to formula II with lithium metal,
In some embodiments, the artificial solid electrolyte layer has a thickness of 5 to 100 nm; and/or the thickness of the pole piece substrate is 5 mu m-1.5 mm.
In some embodiments, the lithium metal-containing composite comprises at least one of a lithium alloy, a lithium boron composite, a porous framework lithium filled metal, a porous framework lithium filled alloy, a porous framework lithium filled boron composite.
In some embodiments, the lithium alloy has the chemical formula LixMyM is selected from at least one of sodium, carbon, silicon, magnesium, aluminum, indium, silver, gold, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, tin, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, cadmium, antimony, hafnium, tantalum, tungsten, rhenium, iridium, platinum, mercury, thallium, lead, bismuth, polonium; x is 0.65 to 0.95, and y is 0.05 to 0.35.
In some embodiments, the lithium boron composite material comprises a composite material with a lithium element and a boron element content of more than 70% by mass, specifically, the lithium boron composite material consists of, in mass percent, 65% to 95% of lithium, 5% to 35% of boron, and 0 to 30% of N selected from at least one of sodium, carbon, silicon, magnesium, aluminum, indium, silver, gold, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, tin, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, cadmium, antimony, hafnium, tantalum, tungsten, rhenium, iridium, platinum, mercury, thallium, lead, bismuth, polonium.
In some embodiments, the porous framework is at least one of copper foam, nickel foam, copper mesh, nickel mesh, carbon cloth, carbon paper powder metallurgy porous copper, powder metallurgy porous nickel, porous stainless steel, porous polymer fiber.
Another object of the present invention is to provide a method for preparing the composite electrode material according to any one of the above embodiments, the method comprising the steps of:
s1, preparation of second polymer: carrying out ring-opening reaction on the styrene maleic anhydride copolymer and (R) - (2, 2-dimethyl-1, 3-dioxolane-4-yl) methylamine to obtain a second polymer;
s2, mixing the second polymer with an organic solvent, and heating for dissolving to obtain a uniform solution;
and S3, soaking the pole piece substrate in the solution for reaction, taking out, drying and removing the solvent to obtain the composite electrode material with the surface coated with the first polymer.
In some embodiments, the organic solvent is N, N-dimethylformamide; preferably, the concentration of the solution is 0.005-100 g/L.
In some embodiments, in step S3, the soaking time is 1-120 min.
In some embodiments, in step S3, the drying temperature is 20 to 80 ℃ and the time is 0.5 to 30 hours.
The present invention also provides a battery comprising the composite electrode material according to any one of the above embodiments or the composite electrode material obtained by the preparation method according to any one of the above embodiments.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the surface of the electrode substrate is coated with the copolymer material containing ether side groups to serve as an artificial solid electrolyte interface to protect the lithium cathode, and the copolymer has high lithium ion conduction rate and strong lithium affinity, can induce lithium ions to be uniformly deposited, and enables the surface of the cathode to be dynamically stable; meanwhile, the reaction of the electrolyte and the lithium cathode is prevented, the lithium cathode interface is stabilized, the consumption and loss of the electrolyte are reduced, the cycle life of the composite electrode material in the ester electrolyte is effectively prolonged, and the cycle life of the energy storage device is prolonged.
(2) The composite electrode material obtained by the method is applied to a lithium battery, and the symmetrical battery is 1 mA/cm2Current density of 1 mAh/cm2The symmetric battery can be cycled for a long time of 700 hours under the condition of specific area capacity and can still keep low polarization voltage (less than 30 mV); li | LiFePO formed by pairing with lithium iron phosphate4The charging and discharging specific capacity of the full battery is 156 mAh/g at the beginning under the multiplying power condition of 1C, no attenuation is generated after the full battery is stably circulated to 200 circles, the coulombic efficiency is always kept at 100%, and the lithium metal battery performance improving effect is good.
(3) The preparation method provided by the invention is simple in process, convenient to prepare and suitable for industrial production.
Drawings
Fig. 1 is a voltage-time curve of pure lithium metal symmetrical batteries manufactured in example 1 and comparative example 1;
FIG. 2 is a graph showing the rate capability of pure lithium metal full cells obtained in example 1 and comparative example 1;
FIG. 3 is a voltage-time curve of lithium boron alloy symmetric cells prepared in example 2 and comparative example 2;
FIG. 4 is a voltage-time curve of the Li-B-Ag alloy symmetrical batteries prepared in example 3 and comparative example 3;
FIG. 5 is a voltage-time curve of the Li-B-Zn alloy symmetrical batteries manufactured in example 4 and comparative example 4;
fig. 6 is a voltage-time curve of the Li-B-Cu alloy symmetric cells prepared in example 5 and comparative example 5.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms than those specifically described herein, and it will be apparent to those skilled in the art that many more modifications are possible without departing from the spirit and scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In the examples of the present invention, the chemical reagents used may be prepared by commercially available or existing preparation methods, and the equipment used is conventional in the art, unless otherwise specified.
In the following examples of the invention, the reaction of the first polymer and the second polymer is shown in the following equation: performing ring-opening reaction on a styrene maleic anhydride copolymer (SMA) and (R) - (2, 2-dimethyl-1, 3-dioxolane-4-yl) methylamine (DMDOL) to obtain a second polymer; dissolving the obtained product in DMF (N, N-dimethylformamide) to react with lithium metal of the negative electrode, generating an artificial solid electrolyte membrane in situ, and drying the intermediate in a vacuum oven to obtain the modified negative electrode:
example 1
SMA and (R) - (2, 2-dimethyl-1, 3 dioxolan-4-yl) methylamine (DMDOL) were mixed at a ratio of 1: 2 (MAn unit: DMDOL), placing in an oil bath at 60 ℃ under vacuum condition for reaction for 24 hours, recrystallizing the product with toluene, and drying the filtrate to obtain styrene ring-opening maleic anhydride (SMA-DMDOL) containing (R) - (2, 2-dimethyl-1, 3 dioxolane-4-yl) methylamine side groups and the product having molecular weight Mn=4319，Mw=7769。
Dissolving the prepared SMA-DMDOL in anhydrous DMF to prepare a 5M solution, putting a thick lithium sheet into the solution, soaking for 30 minutes, taking out, putting into a vacuum oven, and drying to obtain the artificial solid electrolyte interface modified lithium metal cathode containing (R) - (2, 2-dimethyl-1, 3 dioxolane-4-yl) methylamine side group polystyrene open-loop maleic anhydride.
All the above operations are carried out in a glove box.
The modified lithium metal negative electrode was mixed with commercially pure lithium in an electrolyte (1M LiPF)6EMC FEC = 3: 7: 1 (v/v)) at 1 mA/cm2Current density of 1 mAh/cm2The area specific capacity of the battery can reach a long-time cycle of 700 hours and can still keep low polarization voltage (less than 30 mV).
Li | LiFePO formed by pairing modified lithium metal cathode with lithium iron phosphate4The charging and discharging specific capacity of the full battery under the multiplying power condition of 1C is 156 mAh/g at the beginning, no attenuation is generated after the full battery is stably circulated to 200 circles, and the coulomb efficiency is always kept at 100%. The performance in the multiplying power constant current charge-discharge cycle test of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 0.1C is good: the specific capacity is always kept above 150 mAh/g in the small current circulation process, the specific capacity of 135 mAh/g can be kept in stable circulation even under the condition of large current of 5C, and the specific capacity reaches more than 99% of the capacity of the first circle when the specific capacity returns to the multiplying power of 0.1C, so that the good performance of the cathode subjected to surface modification is fully shown; the test results are shown in fig. 1.
Example 2
This example was conducted in a similar parallel experiment as example 1, except that the lithium metal was changed to 84Li-B alloy and the other preparation method was exactly the same as example 1, to obtain an artificial solid electrolyte modified lithium boron alloy negative electrode containing (R) - (2, 2-dimethyl-1, 3 dioxolan-4-yl) methylamine pendant group polystyrene ring-opened maleic anhydride.
The modified lithium boron alloy negative electrode and the bare lithium boron alloy negative electrode are placed in electrolyte (1M LiPF)6EMC FEC = 3: 7: 1 (v/v)) at 1 mA/cm2Current density ofDegree, 1 mAh/cm2The area specific capacity of the battery can reach a long-time circulation of 400 hours and can still keep low polarization voltage (less than 50 mV). The test results are shown in fig. 2.
Example 3
This example was conducted in a similar parallel experiment as example 1, except that lithium metal was changed to a Li-B-Ag alloy, and the other preparation method was exactly the same as example 1, to obtain an artificial solid electrolyte interface-modified Li-B-Ag alloy negative electrode containing (R) - (2, 2-dimethyl-1, 3-dioxolan-4-yl) methylamine pendant group polystyrene ring-opened maleic anhydride.
The modified Li-B-Ag alloy negative electrode and the bare Li-B-Ag alloy negative electrode are placed in electrolyte (1M LiPF)6EMC FEC = 3: 7: 1 (v/v)) at 1 mA/cm2Current density of 10 mAh/cm2The area specific capacity of the symmetrical battery can reach long-time circulation of 800 hours and can still keep low polarization voltage (less than 40 mV). The test results are shown in fig. 3.
Example 4
This example was conducted in a similar parallel fashion to example 1, except that the lithium metal was changed to a Li-B-Zn alloy and the other fabrication methods were exactly the same as example 1, to obtain an artificial solid electrolyte interface-modified Li-B-Zn alloy negative electrode containing (R) - (2, 2-dimethyl-1, 3-dioxolan-4-yl) methylamine pendant group polystyrene ring-opened maleic anhydride.
The modified Li-B-Zn alloy cathode and the bare Li-B-Zn alloy cathode are placed in electrolyte (1M LiPF)6EMC FEC = 3: 7: 1 (v/v)) at 1 mA/cm2Current density of 5 mAh/cm2The area specific capacity of the battery can be prolonged for 1000 hours, and the battery can still keep low polarization voltage (less than 100 mV). The test results are shown in fig. 4.
Example 5
This example was conducted in a similar parallel experiment as example 1, except that lithium metal was changed to a Li-B-Cu alloy, and the other preparation method was exactly the same as example 1, to obtain an artificial solid electrolyte interface-modified Li-B-Cu alloy negative electrode containing (R) - (2, 2-dimethyl-1, 3-dioxolan-4-yl) methylamine pendant group polystyrene ring-opened maleic anhydride.
The modified Li-B-Cu alloy cathode and the bare Li-B-Cu alloy cathode are placed in electrolyte (1M LiPF)6EMC FEC = 3: 7: 1 (v/v)) at 1 mA/cm2Current density of 5 mAh/cm2The area specific capacity of the battery can reach long-time circulation of 1100 hours and can still keep low polarization voltage (less than 50 mV). The test results are shown in fig. 5.
Comparative example 1
Comparative example 1 differs from example 1 in that the lithium metal used is unmodified and the test results are shown in figure 1.
Comparative example 2
Comparative example 2 differs from example 2 in that the lithium boron alloy used is unmodified and the results are shown in figure 2.
Comparative example 3
Comparative example 3 is different from example 3 in that the Li-B-Ag alloy used is not modified, and the test results are shown in fig. 3.
Comparative example 4
Comparative example 4 is different from example 4 in that the Li-B-Zn alloy used is not modified and the test results are shown in fig. 4.
Comparative example 5
Comparative example 5 is different from example 5 in that the Li-B-Cu alloy used is not modified, and the test results are shown in fig. 5.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The composite electrode material is characterized by comprising a pole piece substrate and an artificial solid electrolyte layer coated on the surface of the pole piece substrate, wherein the artificial solid electrolyte layer is composed of a first polymer, and the structure of the first polymer is as shown in formula I:
2. The composite electrode material of claim 1, wherein the first polymer is prepared by reacting a second polymer having a structure of formula II with lithium metal,
3. The composite electrode material according to claim 1, wherein the artificial solid electrolyte layer has a thickness of 5 to 100 nm; and/or the thickness of the pole piece substrate is 5 micrometers-1.5 mm.
4. The composite electrode material of claim 1, wherein the lithium metal-containing composite material comprises at least one of a lithium alloy, a lithium boron composite material, a porous framework lithium-filled metal, a porous framework lithium-filled alloy, and a porous framework lithium boron-filled composite material.
5. A composite electrode material according to claim 4, characterized in that the lithium is alloyedHas a chemical formula of LixMyM is selected from at least one of sodium, carbon, silicon, magnesium, aluminum, indium, silver, gold, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, tin, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, cadmium, antimony, hafnium, tantalum, tungsten, rhenium, iridium, platinum, mercury, thallium, lead, bismuth, polonium; x is 0.65 to 0.95, and y is 0.05 to 0.35.
6. The composite electrode material of claim 4, wherein the lithium boron composite material consists of, in mass percent, 65% to 95% lithium, 5% to 35% boron, and 0 to 30% N selected from at least one of sodium, carbon, silicon, magnesium, aluminum, indium, silver, gold, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, tin, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, cadmium, antimony, hafnium, tantalum, tungsten, rhenium, iridium, platinum, mercury, thallium, lead, bismuth, and polonium.
7. The composite electrode material of claim 4, wherein the porous framework is at least one of copper foam, nickel foam, copper mesh, nickel mesh, carbon cloth, carbon paper, powder metallurgy porous copper, powder metallurgy porous nickel, porous stainless steel, and porous polymer fiber.
8. A method of preparing a composite electrode material according to any one of claims 1 to 7, comprising the steps of:
s1, preparation of second polymer: carrying out ring-opening reaction on the styrene maleic anhydride copolymer and (R) - (2, 2-dimethyl-1, 3-dioxolane-4-yl) methylamine to obtain a second polymer;
s2, mixing the second polymer with an organic solvent, and heating for dissolving to obtain a uniform solution;
and S3, soaking the pole piece substrate in the solution for reaction, taking out, drying and removing the solvent to obtain the composite electrode material with the surface coated with the first polymer.
9. The method for preparing the composite electrode material according to claim 8, wherein the organic solvent is N, N-dimethylformamide, and the solution concentration is 0.005 to 100 g/L.
10. A battery comprising the composite electrode material according to any one of claims 1 to 7.
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Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101740753A (en) * | 2009-12-24 | 2010-06-16 | 苏州星恒电源有限公司 | Lithium battery cathode pole piece |
| CN106876783A (en) * | 2015-12-10 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of all solid state lithium-sulfur cell |
| CN107636204A (en) * | 2015-05-30 | 2018-01-26 | 清洁锂公司 | High-purity lithium and Related product and method |
| CN107645013A (en) * | 2016-07-22 | 2018-01-30 | 中国科学院物理研究所 | Compound quasi-solid electrolyte, its preparation method and the lithium battery or lithium ion battery containing it |
| WO2018237083A1 (en) * | 2017-06-20 | 2018-12-27 | Coreshell Technologies, Inc. | Methods, systems, and compositions for the liquid-phase deposition of thin films onto the surface of battery electrodes |
| CN109167063A (en) * | 2018-08-15 | 2019-01-08 | 广东工业大学 | A kind of lithium anode and its preparation method and application of artificial solid electrolyte interface layer protection |
| CN110635113A (en) * | 2019-08-16 | 2019-12-31 | 南方科技大学 | Lithium cathode or sodium cathode, and preparation method and application of lithium cathode or sodium cathode |
| CN110692152A (en) * | 2017-05-24 | 2020-01-14 | 纳米技术仪器公司 | Alkali metal battery with deformable quasi-solid electrode material |
| CN111463403A (en) * | 2020-04-13 | 2020-07-28 | 武汉大学 | Negative electrode material modified by composite artificial solid electrolyte interface film and battery application thereof |
| WO2020185834A1 (en) * | 2019-03-11 | 2020-09-17 | Coreshell Technologies, Inc. | Solution-phase electrodeposition of artificial solid electrolyte interphase (sei) layers on battery electrodes |
| CN111739935A (en) * | 2020-04-01 | 2020-10-02 | 深圳先进技术研究院 | Inorganic synapse transistor structure and method of fabrication |
| CN111883826A (en) * | 2020-09-09 | 2020-11-03 | 蜂巢能源科技有限公司 | Electrolyte material and preparation method and application thereof |
| CN112635917A (en) * | 2020-12-29 | 2021-04-09 | 浙江大学 | High-strength functional diaphragm for alkali metal-based battery, preparation method of high-strength functional diaphragm and alkali metal-based battery |
| CN112750982A (en) * | 2020-12-30 | 2021-05-04 | 复旦大学 | Laminated lithium metal battery negative electrode material, preparation method thereof and lithium metal secondary battery |
| CN112786957A (en) * | 2019-11-05 | 2021-05-11 | 中天储能科技有限公司 | Polymer solid electrolyte, preparation method thereof and polymer solid battery |
| CN112786842A (en) * | 2021-01-29 | 2021-05-11 | 山东威固新能源科技有限公司 | Alkali metal cathode containing artificial solid electrolyte interface layer and preparation method and application thereof |
| CN112820858A (en) * | 2021-01-07 | 2021-05-18 | 北京理工大学 | Lithium metal negative electrode protected by phosphorus-sulfur-based interfacial film and preparation method thereof |
| WO2021101915A1 (en) * | 2019-11-18 | 2021-05-27 | Coreshell Technologies, Inc. | Solution-phase deposition of thin films on solid-state electrolytes |
| CN113206218A (en) * | 2021-04-23 | 2021-08-03 | 天津中能锂业有限公司 | Lithium ion battery |
| CN113497267A (en) * | 2021-06-04 | 2021-10-12 | 天津中电新能源研究院有限公司 | Solid metal lithium battery and preparation method thereof |
| CN113841267A (en) * | 2019-03-22 | 2021-12-24 | 卡博特公司 | Cathode electrode compositions for battery applications |
-
2022
- 2022-02-23 CN CN202210164558.8A patent/CN114242989B/en active Active
Patent Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101740753A (en) * | 2009-12-24 | 2010-06-16 | 苏州星恒电源有限公司 | Lithium battery cathode pole piece |
| CN107636204A (en) * | 2015-05-30 | 2018-01-26 | 清洁锂公司 | High-purity lithium and Related product and method |
| CN106876783A (en) * | 2015-12-10 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of all solid state lithium-sulfur cell |
| CN107645013A (en) * | 2016-07-22 | 2018-01-30 | 中国科学院物理研究所 | Compound quasi-solid electrolyte, its preparation method and the lithium battery or lithium ion battery containing it |
| CN110692152A (en) * | 2017-05-24 | 2020-01-14 | 纳米技术仪器公司 | Alkali metal battery with deformable quasi-solid electrode material |
| WO2018237083A1 (en) * | 2017-06-20 | 2018-12-27 | Coreshell Technologies, Inc. | Methods, systems, and compositions for the liquid-phase deposition of thin films onto the surface of battery electrodes |
| CN109167063A (en) * | 2018-08-15 | 2019-01-08 | 广东工业大学 | A kind of lithium anode and its preparation method and application of artificial solid electrolyte interface layer protection |
| WO2020185834A1 (en) * | 2019-03-11 | 2020-09-17 | Coreshell Technologies, Inc. | Solution-phase electrodeposition of artificial solid electrolyte interphase (sei) layers on battery electrodes |
| CN113841267A (en) * | 2019-03-22 | 2021-12-24 | 卡博特公司 | Cathode electrode compositions for battery applications |
| CN110635113A (en) * | 2019-08-16 | 2019-12-31 | 南方科技大学 | Lithium cathode or sodium cathode, and preparation method and application of lithium cathode or sodium cathode |
| CN112786957A (en) * | 2019-11-05 | 2021-05-11 | 中天储能科技有限公司 | Polymer solid electrolyte, preparation method thereof and polymer solid battery |
| WO2021101915A1 (en) * | 2019-11-18 | 2021-05-27 | Coreshell Technologies, Inc. | Solution-phase deposition of thin films on solid-state electrolytes |
| CN111739935A (en) * | 2020-04-01 | 2020-10-02 | 深圳先进技术研究院 | Inorganic synapse transistor structure and method of fabrication |
| CN111463403A (en) * | 2020-04-13 | 2020-07-28 | 武汉大学 | Negative electrode material modified by composite artificial solid electrolyte interface film and battery application thereof |
| CN111883826A (en) * | 2020-09-09 | 2020-11-03 | 蜂巢能源科技有限公司 | Electrolyte material and preparation method and application thereof |
| CN112635917A (en) * | 2020-12-29 | 2021-04-09 | 浙江大学 | High-strength functional diaphragm for alkali metal-based battery, preparation method of high-strength functional diaphragm and alkali metal-based battery |
| CN112750982A (en) * | 2020-12-30 | 2021-05-04 | 复旦大学 | Laminated lithium metal battery negative electrode material, preparation method thereof and lithium metal secondary battery |
| CN112820858A (en) * | 2021-01-07 | 2021-05-18 | 北京理工大学 | Lithium metal negative electrode protected by phosphorus-sulfur-based interfacial film and preparation method thereof |
| CN112786842A (en) * | 2021-01-29 | 2021-05-11 | 山东威固新能源科技有限公司 | Alkali metal cathode containing artificial solid electrolyte interface layer and preparation method and application thereof |
| CN113206218A (en) * | 2021-04-23 | 2021-08-03 | 天津中能锂业有限公司 | Lithium ion battery |
| CN113497267A (en) * | 2021-06-04 | 2021-10-12 | 天津中电新能源研究院有限公司 | Solid metal lithium battery and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| An artificial hybrid interphase for an ultrahigh-rate;Anjun Hu etal.;《Energy & Environmental Science》;20210528;第4115-4124页 * |
| Ionic conductive polymers as artificial solid electrolyte interphase films in Li metal batteries – A review;Shilun Gao etal.;《Materials Today》;20201130;第140-159页 * |
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