CN111370678B - Preparation method of modified lithium iron phosphate material for coated lithium battery - Google Patents
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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
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- H—ELECTRICITY
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- 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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- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- 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
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Abstract
The invention discloses a preparation method of a modified lithium iron phosphate material for a coated lithium battery, wherein the surface of lithium iron phosphate is coated with a high-molecular fiber framework, and a nano metal wire is filled in the high-molecular fiber framework; wherein the polymer fiber skeleton is prepared by a melt spinning method. Compared with the traditional compact carbon coating method, the polymer fiber framework coating method adopted by the scheme of the invention has the advantages that the porous modified polymer conductive film can fully fill the holes with the electrolyte, so that the contact area between the electrode and the electrolyte can be increased, the conductivity of lithium iron phosphate is more excellent, and meanwhile, the lithium iron phosphate material has higher compaction density; meanwhile, the coated thermotropic liquid crystal polymer fiber has good non-hygroscopicity, high mechanical physical property at extremely low temperature, moisture resistance and wear resistance and strong low-temperature characteristic, and is favorable for improving the low-temperature performance of the lithium iron phosphate material.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a preparation method of a modified lithium iron phosphate material for a coated lithium battery.
Background
With the decrease of fossil fuel resource supply and the aggravation of environmental deterioration caused by the excessive emission of greenhouse gases, the research and development of new renewable green clean energy sources are more and more important. The lithium ion battery has the advantages of high discharge platform, high specific energy density, light material, wide applicable temperature range and the like, so that the lithium ion battery becomes a secondary battery with wide application prospect. LiFePO as the anode material of Li-ion cell has been proposed by Padhi et al 19974LiFePO from the past4The lithium ion secondary battery has become one of the most potential positive electrode materials of the lithium ion secondary battery due to the advantages of high safety, good stability, low cost, environmental friendliness and the like. However, since lithium iron phosphate itself has weak ion conductivity and electron conductivity, it is usually necessary to modify it。
Surface coating is a common modification method, and in the prior art, some carbon sources are usually added in the lithium iron phosphate synthesis process (such as a hydrothermal method, a sol-gel method, a coprecipitation method and the like) to realize carbon coating modification. Zhang Weixin and the like synthesize LiFePO with controllable appearance by using hydrothermal method4the/C anode material is added with different amounts of sodium dodecyl benzene sulfonate to form LiFePO with controllable appearance4C, such as lithium iron phosphate nano particles, nano rods and nano sheets, the first discharge specific capacities of the three samples under the multiplying power of 0.1C are 145.3 mAh/g, 149.0 mAh/g and 162.9 mAh/g respectively; the specific discharge capacities at 5C rate were 79.3, 100.6 and 129.5 mAh/g (Hydrothermal synthesis of morphology-controlled LiFePO)4Journal of Powersources, 2012, 220: 317-. The Liu and the like take lithium acetate, ferrous chloride and phosphoric acid as raw materials, a sol-gel method is adopted to prepare the lithium iron phosphate nano composite material, the first discharge specific capacity of 0.1C reaches 166 mAh/g after 2.5-4.2V charging and discharging, the specific capacity after 50 cycles is 165 mAh/g, and the retention rate is 99.4% ([ A core-shell LiFePO ]4Journarof Alloys and Compounds, 2013, 574: 155-. Ding et al prepared LiFePO by coprecipitation method4The graphene composite material and the graphene sheet can be used as additives to greatly improve the conductivity of the cathode material. The 0.2C rate discharge capacity reaches 160 mAh/g, the 5C and 10C rate discharge specific capacities are 120 mAh/g and 109 mAh/g respectively, the capacity retention rate is 97 percent after 80 cycles, and good electrochemical performance is shown (Preparation of nano-structured LiFePO)4/graphene composites by co-precipitation method》.Electrochemistry Communications, 2010, 12 (1): 10-13.）。
Although the coating of the method can enable the material to have better charge and discharge performance, an excessively thick compact coating layer is easily formed on the surface of the material, so that the compaction of the material is influenced, and the volume energy density of the material is reduced. The non-uniform coating can reduce the machining performance of the rear-end pole piece manufacturing process, the volume of the active material shrinks under the low-temperature condition, the traditional carbon coating material is easily trapped in a gap formed by the active material, and a continuous conductive channel cannot be formed, so that the cycle and rate performance are greatly reduced under the low-temperature environment.
Therefore, how to ensure the compaction of the material on the basis of improving the electronic conductivity of the lithium iron phosphate cathode material, and improve the low-temperature performance of the material is a direction in which the lithium iron phosphate material needs to be continuously improved.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a modified coated lithium iron phosphate material which has good conductivity and low-temperature performance.
The invention also aims to provide a preparation method of the modified coated lithium iron phosphate material, and the lithium iron phosphate material prepared by the method has good conductivity and good low-temperature performance.
The invention also aims to provide application of the lithium iron phosphate material.
According to the modified coated lithium iron phosphate material provided by the embodiment of the first aspect of the invention, the surface of the lithium iron phosphate is coated with a polymer fiber framework, and a nano metal wire is filled in the polymer fiber framework; wherein the polymer fiber skeleton is prepared by a melt spinning method.
The lithium iron phosphate material provided by the embodiment of the invention has at least the following beneficial effects: according to the scheme, the nano metal wires are filled in the fiber framework, so that the electronic conductivity of the anode material is effectively improved; the crystallinity of the nano metal wire particles is higher, the high polymer material fiber framework obtained by thermal crystallization has high mechanical strength and good chemical stability, the surface part of the fiber framework is not easy to be oxidized, and the fiber framework is not easy to dissolve even if the fiber framework is contacted with electrolyte; the stress damage of the conventional nano metal wire, which is easily caused by volume change in the charging and discharging process, can be relatively relieved under the cladding of the polymer fiber framework structure, so that compared with the traditional compact carbon cladding method, the polymer fiber framework cladding method adopted by the scheme of the invention has the advantages that the porous modified polymer conductive film can fully fill the holes with the electrolyte, the contact area between the electrode and the electrolyte can be increased, the conductivity of the lithium iron phosphate is more excellent, and meanwhile, the lithium iron phosphate material has higher compaction density (up to 2.6 g/cc); meanwhile, the coated thermotropic liquid crystal polymer fiber has good non-hygroscopicity, high mechanical physical property at extremely low temperature, moisture resistance and wear resistance and strong low-temperature characteristic, and is favorable for improving the low-temperature performance of the lithium iron phosphate material.
According to some embodiments of the invention, the polymeric fiber backbone is prepared from poly (4-hydroxybenzoic acid-co-6-hydroxy-2-naphthoic acid) by melt spinning. The polymer fiber material prepared by thermotropic liquid crystal is used as a coating support, and aromatic polyester fiber is combined as a raw material, so that the prepared polymer fiber framework has better low creep property, good non-hygroscopicity, high mechanical physical property at extremely low temperature, humidity resistance and abrasion resistance, the strength is about 6 times of that of common polyester fiber, and the strength is equivalent to that of metal fiber, therefore, when the polymer fiber framework is coated on the surface of the anode material, the structure stability is good, the low-temperature characteristic is strong, the lithium iron phosphate material cannot freeze even at ultralow temperature, the structure of the anode material is favorably stabilized at low temperature, and the exertion of the material capacity is further ensured.
According to some embodiments of the invention, the fineness of the fibers in the polymeric fiber framework is 500 to 800 denier.
According to some embodiments of the invention, the nano-metal wire is selected from a nano-aluminum wire or a nano-copper wire.
The preparation method according to the second aspect embodiment of the present invention comprises the steps of:
s1, preparing a nano metal wire and a polymer fiber framework, and mixing and dispersing the nano metal wire and the polymer fiber framework to obtain a dispersion liquid, wherein the polymer fiber framework is prepared by a melt spinning method;
s2, adding lithium iron phosphate and a silane coupling agent into the dispersion liquid for dispersing connection to obtain a mixed liquid;
and S3, sintering the mixed solution obtained in the step S2 at high temperature in a protective atmosphere to obtain the modified coated lithium iron phosphate material.
The preparation method according to the embodiment of the invention has at least the following beneficial effects: the high polymer material is used as a framework, and the nanowire is filled and then is connected to the surface of the lithium iron phosphate anode material in a dispersing way through the silane coupling agent for modification and coating, so that the low-temperature cycle performance of the lithium iron phosphate can be effectively improved when the nano-wire is applied to the preparation of the lithium iron phosphate anode material.
According to some embodiments of the invention, the polymeric fiber backbone is prepared from poly (4-hydroxybenzoic acid-co-6-hydroxy-2-naphthoic acid) by melt spinning.
According to some embodiments of the invention, the method of preparing the nano-metal wire comprises: carrying out sputtering deposition on a metal foil to obtain an oxide film substrate with the metal, placing the substrate in a solution containing nitrate and a surfactant, reacting for 6-8 h at 70-80 ℃, removing the metal foil from the solution, washing with water, and cooling and drying the eluate to obtain the nano metal wire.
According to some embodiments of the present invention, the sputter deposition is performed by a method selected from at least one of atomic deposition (ALD), radio frequency sputtering, and magnetron sputtering.
According to some embodiments of the invention, the metal oxide thin film has a thickness of 30 to 60 nm.
According to some embodiments of the invention, the nitrate and surfactant containing solution is prepared as follows: mixing 0.1-0.3 part by volume of nitrate solution and 2-4 parts by volume of surfactant, adding into 50-100 parts by volume of water, and performing ultrasonic stirring at 35-45 ℃ to obtain the product; preferably, the ultrasound time is more than 3 min; more preferably, the ultrasonic time is 3-5 min.
According to some embodiments of the invention, the surfactant is a nonionic surfactant; preferably, the nonionic surfactant is selected from polyethylene glycol trimethylnonyl ethers.
According to some embodiments of the invention, the nitrate salt is selected from at least one of potassium nitrate, calcium nitrate or cerium nitrate.
According to some embodiments of the invention, the nitrate is present in an amount of 30 to 40% by weight; preferably 32-38%; more preferably 35%.
According to some embodiments of the present invention, the silane coupling agent is added in step S2 in the form of an aqueous solution (also called a diluent) containing 30 to 40% by mass of the silane coupling agent; preferably, the mass concentration is 32-38%; more preferably 35%.
According to some embodiments of the present invention, the high temperature in the step S3 is 700-900 ℃, and the sintering time is 1-2 h.
According to some embodiments of the invention, the protective atmosphere is selected from at least one of nitrogen or an inert gas.
According to some embodiments of the invention, the inert gas is selected from at least one of helium or argon; more preferably, the inert gas is selected from argon.
According to the application of the embodiment of the third aspect of the invention, the lithium battery comprises a positive electrode material and a negative electrode material, wherein the positive electrode material is the lithium iron phosphate material.
According to the lithium battery provided by the embodiment of the invention, at least the following beneficial effects are achieved: the lithium battery provided by the scheme of the invention has good low-temperature performance and good charge and discharge performance.
Drawings
Fig. 1 is an SEM image of lithium iron phosphate prepared in example 1 of the present invention;
fig. 2 is an SEM image of lithium iron phosphate in comparative example 1 of the present invention;
fig. 3 is a diagram showing the results of low-temperature cycle performance tests of lithium iron phosphate in examples 1 to 3 of the present invention and comparative example 1.
Detailed Description
In order to explain technical contents, achieved objects, and effects of the present invention in detail, the following description is made with reference to the accompanying drawings in combination with the embodiments. The test methods used in the examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available reagents and materials unless otherwise specified.
The first embodiment of the invention is as follows: a preparation method for modifying and coating a lithium iron phosphate positive electrode material comprises the following specific steps:
(1) 0.2mL of 35% potassium nitrate solution and 3mL of a surfactant Tergitol TMN 10 (polyethylene glycol trimethyl nonyl ether (C)12H26O.(C2H4O)nAnd n is more than 0), adding the mixture into 80ml of deionized water, and carrying out ultrasonic stirring for 4 minutes at the temperature of 40 ℃.
(2) And (2) placing a metal oxide film substrate with the thickness of 45nm, which is subjected to atomic layer deposition on the copper foil, into the solution obtained in the step (1), and heating at the temperature of 75 ℃ for 7 hours. And then removing the copper foil from the solution, cleaning the copper foil by deionized water, and naturally cooling and drying the copper foil.
(3) The polymer material poly (4-hydroxybenzoic acid-co-6-hydroxy-2-naphthoic acid) (Tianjin Xiansi Biotechnology Co., Ltd., cas No. 70679-92-4) was prepared into a fiber skeleton by a melt spinning method (at 150 ℃ C.) and the fiber fineness was about 700 denier.
(4) Mixing and dispersing the nano metal wire prepared in the step (2) and the fiber framework obtained in the step (3) according to the mass ratio of 1:1 to obtain a dispersion liquid (the material concentration is 75 g/ml), adding 220g of lithium iron phosphate material powder, and adding 35% of C11H24O6And after Si (silane coupling agent) (the mass ratio of the dispersion liquid to the lithium iron phosphate to the silane coupling agent is 1.5:7.5: 1) is subjected to dispersion connection, sintering the obtained solution for 1.5h at 800 ℃ in a nitrogen atmosphere, and naturally cooling to obtain the lithium iron phosphate cathode material coated with the polymer fiber framework filled with the nanowires.
The second embodiment of the invention is as follows: a preparation method for modifying and coating a lithium iron phosphate positive electrode material comprises the following specific steps:
(1) 0.1mL of 35% calcium nitrate solution and 2mL of a surfactant Tergitol TMN 10 (polyethylene glycol trimethyl nonyl ether (C)12H26O.(C2H4O)nN is more than 0), adding into 50ml deionized water, and ultrasonically stirring at 35 deg.CStirring for 3 minutes.
(2) And (2) placing a metal oxide film substrate with the thickness of 30nm, which is subjected to atomic layer deposition on the copper foil, into the solution obtained in the step (1), and heating at the temperature of 70 ℃ for 6 hours. And then removing the copper foil from the solution, cleaning the copper foil by deionized water, and naturally cooling and drying the copper foil.
(3) The polymer material poly (4-hydroxybenzoic acid-co-6-hydroxy-2-naphthoic acid) (Tianjin Xiansi Biotechnology Co., Ltd., cas No. 70679-92-4) was prepared into a fiber skeleton by a melt spinning method (at 150 ℃ C.) and the fiber fineness was about 500 denier.
(4) Mixing and dispersing the nano metal wire prepared in the step (2) and the fiber framework obtained in the step (3) according to the mass ratio of 1:1 to obtain a dispersion liquid (the material concentration is 75 g/ml), adding 200g of lithium iron phosphate material powder, and adding 35% of C11H24O6And dispersing and linking with an Si silane coupling agent (the mass ratio of the dispersion liquid to the lithium iron phosphate to the silane coupling agent is 1.5:7.5: 1). And sintering the mixed solution for 1h at 700 ℃ in an argon atmosphere, and naturally cooling to obtain the lithium iron phosphate cathode material coated with the polymer fiber framework filled with the nanowires.
The third embodiment of the invention is as follows: a preparation method of an iron phosphate precursor and a lithium iron phosphate cathode material comprises the following steps:
(1) 0.3mL of 35% cerium nitrate solution and 4mL of surfactant Tergitol TMN 10 (polyethylene glycol trimethyl nonyl ether (C)12H26O.(C2H4O)nAnd n is more than 0), adding the mixture into 100ml of deionized water, and ultrasonically stirring the mixture for 5 minutes at the temperature of between 35 and 45 ℃.
(2) And (2) placing a metal oxide film substrate with the thickness of 60nm, which is subjected to atomic layer deposition on the aluminum foil, into the solution in the step (1), and heating at the temperature of 80 ℃ for 8 hours. And then removing the aluminum foil from the solution, washing the aluminum foil by deionized water, and naturally cooling and drying the aluminum foil.
(3) The polymer material poly (4-hydroxybenzoic acid-co-6-hydroxy-2-naphthoic acid) (Tianjin Xiansi Biotechnology Co., Ltd., cas No. 70679-92-4) was prepared into a fiber skeleton by a melt spinning method (at 150 ℃ C.) and the fiber fineness was about 800 denier.
(4) Mixing and dispersing the nano metal wire prepared in the step (2) and the fiber framework obtained in the step (3) according to the mass ratio of 1:1 to obtain a dispersion liquid (the material concentration is 75 g/ml), adding 250g of lithium iron phosphate material powder, and adding 35% of C11H24O6And dispersing and linking with an Si silane coupling agent (the mass ratio of the dispersion liquid to the lithium iron phosphate to the silane coupling agent is 1.5:7.5: 1). And sintering the mixed solution for 2h at 900 ℃ in a nitrogen atmosphere, and naturally cooling to obtain the lithium iron phosphate cathode material coated with the polymer fiber framework filled with the nanowires.
The first comparative example of the invention is: a lithium iron phosphate material, which is an unmodified coated lithium iron phosphate material powder from the same source as in example 1.
Scanning Electron Microscope (SEM) characterization was performed on the modified coated lithium iron phosphate material prepared in example 1 and the lithium iron phosphate material in comparative example 1, and the results are shown in fig. 1 and 2. As can be seen from fig. 1, the lithium iron phosphate material prepared by the embodiment of the invention has a smooth surface and a good coating effect. As can be seen from fig. 2, the unmodified lithium iron phosphate material has a rough surface and obvious interparticle agglomeration. The lithium iron phosphate sample coated and modified in the embodiment 1 has a smooth surface and a good coating effect.
The shape and performance of the lithium iron phosphate material prepared in other embodiments are characterized, and the results are similar to those of embodiment 1 and are not repeated herein.
The modified coated lithium iron phosphate material prepared in examples 1 to 3 and the lithium iron phosphate sample in comparative example 1 were prepared into a 32135 cylindrical battery according to a conventional method under the same conditions, and the electrochemical cycle performance of the prepared cylindrical battery was tested at-20 ℃, and the results are shown in fig. 3. As can be seen from the results in fig. 3, the lithium iron phosphate materials prepared in embodiments 1 to 3 of the present invention have a significantly better low-temperature performance than the uncoated lithium iron phosphate in comparative example 1, the lithium iron phosphate materials prepared in embodiments 1 to 3 still have a capacity retention rate of about 90% after 350 cycles, and the cycle performance of the product in comparative example 1 is reduced to less than 80% after about 280 cycles, which indicates that the lithium iron phosphate material prepared in the embodiment of the present invention has a good low-temperature performance.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to the related technical fields, are included in the scope of the present invention.
Claims (10)
1. A preparation method of a modified lithium iron phosphate material for a coated lithium battery is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing a nano metal wire and a polymer fiber framework, and mixing and dispersing the nano metal wire and the polymer fiber framework to obtain a dispersion liquid, wherein the polymer fiber framework is prepared by a melt spinning method;
s2, adding lithium iron phosphate and a silane coupling agent into the dispersion liquid for dispersing connection to obtain a mixed liquid;
s3, sintering the mixed solution obtained in the step S2 at high temperature in a protective atmosphere to obtain the modified coated lithium iron phosphate material; wherein the polymer fiber skeleton is prepared from poly (4-hydroxybenzoic acid-co-6-hydroxy-2-naphthoic acid) by a melt spinning method.
2. The method of claim 1, wherein: the preparation method of the nano metal wire comprises the following steps: carrying out sputtering deposition on the metal foil to obtain a base material with a metal oxide film, placing the base material in a solution containing nitrate and a surfactant, reacting for 6-8 h at 70-80 ℃, removing the metal foil from the solution, washing with water, and cooling and drying to obtain the nano metal wire.
3. The method of claim 2, wherein: the thickness of the metal oxide film is 30-60 nm.
4. The method of claim 2, wherein: the preparation method of the solution containing the nitrate and the surfactant comprises the following steps: mixing 0.1-0.3 part by volume of nitrate solution and 2-4 parts by volume of surfactant, adding into 50-100 parts by volume of water, and performing ultrasonic stirring at 35-45 ℃ to obtain the product.
5. The method of claim 4, wherein: the ultrasonic treatment time is more than 3 min.
6. The method of claim 5, wherein: the ultrasonic time is 3-5 min.
7. The method of claim 1, wherein: in the step S2, the silane coupling agent is added in the form of a diluent containing 30-40% by mass of the silane coupling agent.
8. The method of claim 7, wherein: the mass concentration of the silane coupling agent is 32-38%.
9. The method of claim 8, wherein: the mass concentration of the silane coupling agent was 35%.
10. The method of claim 1, wherein: the high temperature in the step S3 is 700-900 ℃, and the sintering time is 1-2 h.
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Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9093693B2 (en) * | 2009-01-13 | 2015-07-28 | Samsung Electronics Co., Ltd. | Process for producing nano graphene reinforced composite particles for lithium battery electrodes |
| JP6358493B2 (en) * | 2011-11-15 | 2018-07-18 | デンカ株式会社 | Composite particle, method for producing the same, electrode material for secondary battery, and secondary battery |
| US20130171502A1 (en) * | 2011-12-29 | 2013-07-04 | Guorong Chen | Hybrid electrode and surface-mediated cell-based super-hybrid energy storage device containing same |
| CN103545525B (en) * | 2012-07-17 | 2016-02-24 | 南京宏德纳米材料有限公司 | Lithium ion cell nano compound positive and negative electrode material containing three dimensions conductive network and preparation method |
| KR101464369B1 (en) * | 2012-09-26 | 2014-11-21 | 주식회사 포스코이에스엠 | Method for the preparation of a lithium iron phosphate of olivine crystal structure and carbon-coated lithium iron phosphate of olivine crystal structure prepared thereby, including carbon inside |
| CN103531814B (en) * | 2013-10-28 | 2015-03-25 | 深圳格林德能源有限公司 | Composite conductive agent and dispersion method thereof as well as positive plate and lithium ion battery |
| US10361460B2 (en) * | 2015-10-02 | 2019-07-23 | Nanotek Instruments, Inc. | Process for producing lithium batteries having an ultra-high energy density |
| EP3154111B1 (en) * | 2015-10-07 | 2019-06-12 | VARTA Microbattery GmbH | Composite material, electrode, method to produce the material and the electrode and electrochemical cell comprising the electrode |
| US20170125802A1 (en) * | 2015-10-28 | 2017-05-04 | The Regents Of The University Of California | Methods for making conformational conductive coated materials |
| KR20170056310A (en) * | 2015-11-13 | 2017-05-23 | 주식회사 엘지화학 | Cable-type secondary battery |
| CN106340395A (en) * | 2016-10-21 | 2017-01-18 | 苏州捷迪纳米科技有限公司 | Fibrous composite electrode material and preparation method thereof |
| US10985373B2 (en) * | 2017-02-27 | 2021-04-20 | Global Graphene Group, Inc. | Lithium battery cathode and method of manufacturing |
| KR101815212B1 (en) * | 2017-03-22 | 2018-01-05 | 한국과학기술원 | Fiber Woven Fabric Based Structural Battery Composites |
| US10483533B2 (en) * | 2017-04-10 | 2019-11-19 | Global Graphene Group, Inc. | Encapsulated cathode active material particles, lithium secondary batteries containing same, and method of manufacturing |
| US20190173079A1 (en) * | 2017-12-05 | 2019-06-06 | Nanotek Instruments, Inc. | Method of Producing Participate Electrode Materials for Alkali Metal Batteries |
| CN108735997B (en) * | 2018-05-28 | 2021-07-20 | 贝特瑞（天津）纳米材料制造有限公司 | Lithium iron phosphate-based composite material, and preparation method and application thereof |
| CN109524658A (en) * | 2018-12-06 | 2019-03-26 | 深圳市德方纳米科技股份有限公司 | Anode material for lithium-ion batteries and preparation method thereof and lithium ion battery |
| CN109860603B (en) * | 2019-01-21 | 2022-01-28 | 珠海冠宇电池股份有限公司 | Lithium battery pole piece, preparation method thereof and lithium battery |
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