CN114181240B - Preparation method of lithium bis (oxalato) borate - Google Patents
Preparation method of lithium bis (oxalato) borate Download PDFInfo
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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Abstract
The invention provides a preparation method of lithium bisoxalato borate, and belongs to the technical field of special chemicals. The method comprises the following steps: 1) Mixing a lithium source, boric acid and an oxalic acid compound, and performing ball milling to obtain a mixed material; 2) And (3) spreading the mixed material in a microwave hot-pressing device, and performing microwave hot-pressing reaction to obtain the lithium bisoxalato borate. The preparation method provided by the invention has the advantages of high reaction efficiency, high yield, low water content and high purity of the prepared lithium bisoxalato borate.
Description
Technical Field
The invention belongs to the technical field of special chemicals, and particularly relates to a preparation method of lithium bisoxalato borate.
Background
The lithium borate complex is a novel lithium ion battery electrolyte, and is most represented by lithium bisoxalato borate LiBOB. The lithium bisoxalato borate is a coordination chelate, and forms larger anions in the electrolyte, smaller lattice energy and more ions in the solvent, thereby improving the conductivity of the electrolyte. The lithium bisoxalato borate (LiBOB) has good electrochemical stability and thermal stability, can react with a specific solvent to form a stable SEI film, and can be subjected to repeated cycling energy without attenuation and hexafluoroLithium phosphate has higher thermal stability than that of the lithium phosphate and the decomposed product B 2 O 3 And CO 2 The electrolyte has little influence on the service performance and environment of the battery, and is an electrolyte substance with development potential in the lithium battery industry.
The prior synthesis method of the lithium bisoxalato borate comprises an aqueous phase method, a solid phase method and a solvent method. The solvent method adopts an organic solvent as a reaction medium, increases the cost of raw materials and has pollution to the environment. The aqueous phase method requires long time for removing water, and has long reaction time and low efficiency. Patent CN107602603a discloses a method for synthesizing lithium bisoxalato borate by a solid phase method, which requires a reaction in a nitrogen atmosphere, and has the advantages of high energy consumption and long reaction time. Therefore, how to increase the efficiency of synthesis and reduce the synthesis time is a key challenge facing current work.
Disclosure of Invention
The invention provides a preparation method of lithium bisoxalato borate, which has the advantages of high reaction efficiency, high yield, low water content and high purity of the prepared lithium bisoxalato borate.
In order to achieve the above purpose, the invention provides a preparation method of lithium bisoxalato borate, comprising the following steps:
1) Mixing a lithium source, boric acid and an oxalic acid compound, and performing ball milling to obtain a mixed material;
2) And (3) spreading the mixed material in a microwave hot-pressing device, and performing microwave hot-pressing reaction to obtain the lithium bisoxalato borate.
Preferably, the molar ratio of the lithium source, the boron source and the oxalic acid compound is 0.8-1.1:0.8-1.2:2.0-2.3.
Preferably, the ball milling time is 25-35 min; the rotating speed is 90-110 r/min.
Preferably, the pressure of the microwave hot-pressing reaction is 0.1-20 Mpa.
Preferably, the time of the microwave hot-pressing reaction is 5-100 min.
Preferably, the microwave power of the microwave hot-pressing reaction is 100-500 w.
Preferably, the temperature of the microwave hot-pressing reaction is 100-240 ℃.
Preferably, the microwave hot pressing device comprises a pressing upper pressing plate, a pressing lower pressing plate and a microwave transmitting plate; a trough is arranged in the tabletting lower pressing plate; the microwave transmitting plate is arranged at the lower part of the pressing plate upper pressing plate, is integrated with the pressing plate upper pressing plate, and is matched with the pressing plate lower pressing plate trough.
Preferably, when the microwave hot-pressing reaction is carried out, the pressing rate of the upper pressing plate and the lower pressing plate of the microwave hot-pressing device is 0.1-100 mm/s.
Preferably, the method further comprises dissolving the lithium bisoxalato borate with an organic solvent, filtering, concentrating and drying.
Compared with the prior art, the invention has the advantages and positive effects that:
according to the preparation method of the lithium bisoxalato borate, the lithium source, the boron source and the oxalic acid compound are mixed and ball-milled, the mixed materials are subjected to microwave hot-pressing reaction by adopting the microwave hot-pressing device, the microwave hot-pressing reaction can be directly carried out in the compacting process, the preparation method can be completed in one step, the time and the labor are saved, the preparation process steps are reduced, the operation process is simple, and the preparation method is suitable for industrial production. Meanwhile, in the hot pressing process, the solid particles of the raw materials can be fully contacted, so that the reaction efficiency and the conversion rate are improved.
The microwave hot pressing method combines compaction and heating reaction together, and can timely press out water generated by the reaction, thereby reducing the water content of the product.
The microwave can be used for heating rapidly and uniformly, and the microwave can enable the molecules to vibrate to increase intermolecular friction, so that the reaction efficiency is improved. Meanwhile, microwaves can play a magnetic effect to promote the selective reaction among reactant ions, and no side reaction is generated; and microwaves have an electric effect, so that the activation energy of the reaction is reduced, and the reaction is accelerated.
Meanwhile, the lithium bisoxalato borate prepared by the method has high purity and extremely low moisture, and can omit the steps of cooling, crystallizing, filtering and drying, thereby preventing moisture from being introduced in the recrystallization and filtration process.
Drawings
FIG. 1 is a schematic diagram of a microwave hot press apparatus used in the present invention;
FIG. 2 is an XRD pattern of lithium bisoxalato borate of examples 1 to 8 and comparative examples 1 to 5;
wherein: 1-base 1, 2-tabletting lower pressure plate, 3-tabletting upper pressure plate, 4-trough, 5-vacuum pipeline, 6-vacuum pump, 7-telescopic link 7, 8-microwave transmitting plate, 9-microwave transmitter, 10-pressure sensor, 11-pressure system, 12-digital display operation screen, 13-pressure system switch, 14-vacuum system switch, 15-microwave heating system switch, 16-scram button, 17-sieve mesh base, 18-outlet, 19-conversion valve.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of lithium bisoxalato borate, which comprises the following steps:
1) Mixing a lithium source, a boron source and an oxalic acid compound, and performing ball milling to obtain a mixed material;
2) And (3) spreading the mixed material in a microwave hot-pressing device, and performing microwave hot-pressing reaction to obtain the lithium bisoxalato borate.
The invention mixes the lithium source, boric acid and oxalic acid compound for ball milling to obtain the mixed material. In the present invention, the lithium source is preferably one or more of lithium oxalate, lithium carbonate, lithium hydroxide and lithium tetrafluoroborate; more preferably lithium oxalate and lithium hydroxide; most preferred is lithium hydroxide.
In the present invention, the boron source is preferably one or more of anhydrous boric acid, boric acid dihydrate, boric acid monohydrate and lithium borate; more preferably anhydrous boric acid.
In the present invention, the oxalic acid compound is preferably one or more of lithium oxalate, potassium oxalate, ammonium oxalate, oxalic acid amide, anhydrous oxalic acid, hydrated oxalic acid, rubidium oxalate or cesium oxalate, more preferably anhydrous oxalic acid, hydrated oxalic acid, and most preferably anhydrous oxalic acid.
In the present invention, the molar ratio of the lithium source, boric acid and oxalic acid compound is preferably 0.8 to 1.1:0.8 to 1.2:2.0 to 2.3, more preferably 1:1:2.1.
The source of the lithium source, the boron source and the oxalic acid compound is not particularly limited, and the conventional commercial products in the art can be adopted.
In the invention, the rotating speed of the ball milling is preferably 90-110 r/min, more preferably 100r/min; the ball milling time is preferably 25 to 35 minutes, more preferably 30 minutes. According to the invention, the lithium source, the boron source and the oxalic acid are ball-milled, so that the materials can be fully mixed.
After the mixed material is obtained, the mixed material is tiled in a microwave hot-pressing device, and microwave hot-pressing reaction is carried out to obtain the lithium bisoxalato borate.
In the present invention, the pressure of the microwave hot-pressing reaction is preferably 0.1 to 20Mpa, more preferably 5 to 15Mpa.
In the present invention, the time of the microwave hot-pressing reaction is preferably 5 to 100 minutes, more preferably 10 to 15 minutes.
In the present invention, the microwave power of the microwave hot-pressing reaction is preferably 100 to 500w, more preferably 150 to 200w.
In the present invention, the temperature of the microwave hot-pressing reaction is preferably 100 to 240 ℃, more preferably 120 to 200 ℃.
In the invention, the microwave hot pressing device preferably comprises a pressing upper pressing plate, a pressing lower pressing plate and a microwave transmitting plate; a trough is arranged in the tabletting lower pressing plate; the microwave transmitting plate is arranged at the lower part of the pressing plate upper pressing plate, is integrated with the pressing plate upper pressing plate, and is matched with the pressing plate lower pressing plate trough. As particularly shown in fig. 1.
In the present invention, the pressing rate of the upper pressing plate and the lower pressing plate of the microwave hot pressing apparatus is preferably 0.1 to 100mm/s, more preferably 0.5 to 10mm/s, when the microwave hot pressing reaction is performed.
The invention adopts the microwave hot-pressing device to carry out microwave hot-pressing reaction on the mixed materials, and can lead the solid particles of the raw materials to be fully contacted in the hot-pressing process, thereby improving the conversion rate and the reaction efficiency. The microwave can be used for heating rapidly and uniformly, and the microwave can enable the molecular vibration to increase intermolecular friction, so that the reaction efficiency is improved. Meanwhile, microwaves can play a magnetic effect to promote the selective reaction among reactant ions, and no side reaction is generated; and microwaves have an electric effect, so that the activation energy of the reaction is reduced, and the reaction is accelerated. In conclusion, the invention adopts the microwave hot-pressing method, which not only can improve the reaction efficiency and shorten the reaction time, but also is beneficial to improving the yield and purity. Meanwhile, the method is adopted to simultaneously operate heating and pressurizing, the reaction can be completed in one step, and the operation is simpler.
After obtaining the lithium bisoxalato borate, the invention preferably further comprises the step of purifying the lithium bisoxalato borate. The purification method is preferably dissolution with an organic solvent, filtration, concentration and drying.
In the present invention, the organic solvent is preferably any one or a mixture of several of dimethyl carbonate, dipropyl carbonate, ethylene propylene carbonate, vinylene carbonate, ethylene isopropyl carbonate, methyl butyl carbonate, dibutyl carbonate, ethylene butyl carbonate, propylene carbonate, methyl ethyl carbonate, diethyl carbonate, ethyl acetate, acetonitrile, propionitrile, butyronitrile, tetrahydrofuran and dimethyl tetrahydrofuran, more preferably ethyl acetate and/or acetonitrile.
In the invention, the drying mode is preferably rotary evaporation drying; the specific operation of spin drying is preferably to spin evaporate the concentrated solution at 60 ℃ until no liquid exists, and then to heat up to 180 ℃ for spin evaporation.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
Adding 7.18g of lithium hydroxide, 18.55g of anhydrous boric acid and 56.7g of anhydrous oxalic acid into a ball milling tank, performing ball milling, dispersing and mixing uniformly for 30min at a ball milling speed of 100r/min to obtain a mixture A;
and (3) spreading the mixture A in a microwave hot-pressing die, wherein the microwave heating power is 100W, the hot-pressing pressure is 10MPa, the microwave hot-pressing temperature is 100 ℃, and the hot-pressing time is 10min, so as to obtain a crude product B.
The crude product B was dissolved in 200g of ethyl acetate, and then filtered and concentrated to give a concentrated solution C.
And (3) rotationally evaporating the obtained concentrated solution C at 60 ℃ until no liquid exists, and rotationally evaporating the concentrated solution C at 180 ℃ for 6 hours to obtain the high-purity lithium bisoxalato borate.
Example 2
Adding 7.18g of lithium hydroxide, 18.55g of anhydrous boric acid and 56.7g of anhydrous oxalic acid into a ball milling tank, performing ball milling, dispersing and mixing uniformly for 30min at a ball milling speed of 100r/min to obtain a mixture A;
spreading the mixture A in a hot-pressing die, heating with microwave with power of 200W and hot-pressing pressure of 10Mpa, and hot-pressing temperature of 100deg.C for 10min to obtain crude product B.
The crude product B was dissolved in 200g of ethyl acetate, and then filtered and concentrated to give a concentrated solution C.
And (3) rotationally evaporating the obtained concentrated solution C at 60 ℃ until no liquid exists, and rotationally evaporating the concentrated solution C at 180 ℃ for 6 hours to obtain the high-purity lithium bisoxalato borate.
Example 3
Adding 7.18g of lithium hydroxide, 18.55g of anhydrous boric acid and 56.7g of anhydrous oxalic acid into a ball milling tank, performing ball milling, dispersing and mixing uniformly for 30min at a ball milling speed of 100r/min to obtain a mixture A;
spreading the mixture A in a hot-pressing die, wherein the microwave heating power is 100W, the hot-pressing pressure is 10MPa, the hot-pressing temperature is 100 ℃, and the hot-pressing time is 15min, so as to obtain a crude product B.
The crude product B was dissolved in 200g of ethyl acetate, and then filtered and concentrated to give a concentrated solution C.
And (3) rotationally evaporating the obtained concentrated solution C at 60 ℃ until no liquid exists, and rotationally evaporating the concentrated solution C at 180 ℃ for 6 hours to obtain the high-purity lithium bisoxalato borate.
Example 4
Adding 7.18g of lithium hydroxide, 18.55g of anhydrous boric acid and 56.7g of anhydrous oxalic acid into a ball milling tank, performing ball milling, dispersing and mixing uniformly for 30min at a ball milling speed of 100r/min to obtain a mixture A;
spreading the mixture A in a hot-pressing die, heating by microwaves at 100W, and heating at 5Mpa for 10min at 100 ℃ to obtain a crude product B.
The crude product B was dissolved in 200g of ethyl acetate, and then filtered and concentrated to give a concentrated solution C.
And (3) rotationally evaporating the obtained concentrated solution C at 60 ℃ until no liquid exists, and rotationally evaporating the concentrated solution C at 180 ℃ for 6 hours to obtain the high-purity lithium bisoxalato borate.
Example 5
Adding 7.18g of lithium hydroxide, 18.55g of anhydrous boric acid and 56.7g of anhydrous oxalic acid into a ball milling tank, performing ball milling, dispersing and mixing uniformly for 30min at a ball milling speed of 100r/min to obtain a mixture A;
spreading the mixture A in a hot-pressing die, heating with microwave at 100W, and hot-pressing at 5Mpa and 120 ℃ for 10min to obtain a crude product B.
The crude product B was dissolved in 200g of ethyl acetate, and then filtered and concentrated to give a concentrated solution C.
And C, rotationally evaporating the concentrated solution C obtained in the step C at the temperature of 60 ℃ until no liquid exists, and rotationally evaporating the concentrated solution C at the temperature of 150 ℃ for 6 hours to obtain the high-purity lithium bisoxalato borate.
Example 6
Adding 7.18g of lithium hydroxide, 18.55g of anhydrous boric acid and 56.7g of anhydrous oxalic acid into a ball milling tank, performing ball milling, dispersing and mixing uniformly for 30min at a ball milling speed of 100r/min to obtain a mixture A;
spreading the mixture A in a hot-pressing die, heating by microwaves at 100W, and heating at 5Mpa for 5min at 100 ℃ to obtain a crude product B.
The crude product B was dissolved in 200g of ethyl acetate, and then filtered and concentrated to give a concentrated solution C.
And (3) rotationally evaporating the obtained concentrated solution C at the temperature of 60 ℃ until no liquid exists, and rotationally evaporating the concentrated solution C at the temperature of 180 ℃ for 3 hours to obtain the high-purity lithium bisoxalato borate.
Example 7
Adding 30.57g of lithium oxalate, 19.2g of lithium borate and 99.72g of potassium oxalate into a ball milling tank, performing ball milling, dispersing and mixing uniformly, performing ball milling for 35min, and performing ball milling at a speed of 90r/min to obtain a mixture A;
spreading the mixture A in a microwave hot-pressing die, wherein the microwave heating power is 500W, the hot-pressing pressure is 0.1MPa, the microwave hot-pressing temperature is 240 ℃, and the hot-pressing time is 100min, so as to obtain a crude product B.
The crude product B was dissolved in 200g of ethyl acetate, and then filtered and concentrated to give a concentrated solution C.
And (3) rotationally evaporating the obtained concentrated solution C at 60 ℃ until no liquid exists, and rotationally evaporating the concentrated solution C at 180 ℃ for 6 hours to obtain the high-purity lithium bisoxalato borate.
Example 8
Adding 30.57g of lithium oxalate, 21.6g of boric acid monohydrate and 110.52g of potassium oxalate hydrate into a ball milling tank, performing ball milling, dispersing and mixing uniformly, wherein the ball milling time is 25min, and the ball milling speed is 110r/min to obtain a mixture A;
and (3) spreading the mixture A in a microwave hot-pressing die, wherein the microwave heating power is 300W, the hot-pressing pressure is 20MPa, the microwave hot-pressing temperature is 100 ℃, and the hot-pressing time is 50min, so as to obtain a crude product B.
The crude product B was dissolved in 200g of ethyl acetate, and then filtered and concentrated to give a concentrated solution C.
And (3) rotationally evaporating the obtained concentrated solution C at 60 ℃ until no liquid exists, and rotationally evaporating the concentrated solution C at 180 ℃ for 6 hours to obtain the high-purity lithium bisoxalato borate.
Comparative example 1
The procedure is as in example 5, except that: the specific operation is as follows without microwave treatment:
adding 7.18g of lithium hydroxide, 18.55g of anhydrous boric acid and 56.7g of anhydrous oxalic acid into a ball milling tank, performing ball milling, dispersing and mixing uniformly for 30min at a ball milling speed of 100r/min to obtain a mixture A;
spreading the mixture A in a tablet press die, pressing into tablets under the pressure of 10Mpa, reacting the materials pressed into tablets at 120 ℃ for 6 hours, heating to 240 ℃ and reacting for 6 hours to obtain a crude product B.
The crude product B was dissolved in 200g of ethyl acetate, and then filtered and concentrated to give a concentrated solution C.
And (3) rotationally evaporating the obtained concentrated solution C at the temperature of 60 ℃ until no liquid exists, and rotationally evaporating the concentrated solution C at the temperature of 180 ℃ for 3 hours to obtain the high-purity lithium bisoxalato borate.
Comparative example 2
The procedure is as in example 5, except that: the tablet pressing treatment is not carried out, and the specific operation is as follows:
adding 7.18g of lithium hydroxide, 18.55g of anhydrous boric acid and 56.7g of anhydrous oxalic acid into a ball milling tank, performing ball milling, dispersing and mixing uniformly for 30min at a ball milling speed of 100r/min to obtain a mixture A;
spreading the mixture A in a tablet press die, setting the pressurizing pressure to be 0MPa, and heating the mixture A by microwaves at 120 ℃ for 10 minutes at 100W to obtain a crude product A.
The crude product A was dissolved in 200g of ethyl acetate, and then filtered and concentrated to give a concentrated solution B.
And (3) rotationally evaporating the obtained concentrated solution B at the temperature of 60 ℃ until no liquid exists, and rotationally evaporating the concentrated solution B at the temperature of 180 ℃ for 3 hours to obtain the high-purity lithium bisoxalato borate.
Comparative example 3
The procedure is as in example 5, except that: the grinding treatment is not carried out, and the specific operation is as follows:
7.18g of lithium hydroxide, 18.55g of anhydrous boric acid and 56.7g of anhydrous oxalic acid are tiled in a microwave hot-pressing die, the microwave heating power is 100W, the hot-pressing pressure is 10MPa, the microwave hot-pressing temperature is 120 ℃, and the hot-pressing time is 10min, so that a crude product B is obtained.
The crude product B was dissolved in 200g of ethyl acetate, and then filtered and concentrated to give a concentrated solution C.
And (3) rotationally evaporating the obtained concentrated solution C at 60 ℃ until no liquid exists, and rotationally evaporating the concentrated solution C at 180 ℃ for 6 hours to obtain the high-purity lithium bisoxalato borate.
Comparative example 4
The procedure is as in example 5, except that: no grinding and tabletting treatment was performed, and the specific operations were as follows:
7.18g of lithium hydroxide, 18.55g of anhydrous boric acid and 56.7g of anhydrous oxalic acid are tiled in a microwave hot-pressing die, the microwave heating power is 100W, the microwave heating temperature is 120 ℃, and the microwave time is 10min, so that a crude product B is obtained.
The crude product B was dissolved in 200g of ethyl acetate, and then filtered and concentrated to give a concentrated solution C.
And (3) rotationally evaporating the obtained concentrated solution C at 60 ℃ until no liquid exists, and rotationally evaporating the concentrated solution C at 180 ℃ for 6 hours to obtain the high-purity lithium bisoxalato borate.
Comparative example 5
The procedure is as in example 5, except that: the tabletting and microwave reaction are separately operated, and the specific operation is as follows:
adding 7.18g of lithium hydroxide, 18.55g of anhydrous boric acid and 56.7g of anhydrous oxalic acid into a ball milling tank, performing ball milling, dispersing and mixing uniformly for 30min at a ball milling speed of 100r/min to obtain a mixture A;
spreading the mixture A in a microwave hot-pressing die, pressing into tablets under the pressure of 10Mpa, performing microwave heating reaction on the materials pressed into tablets, wherein the microwave heating power is 100W, and the microwave heating temperature is 120 ℃ for 10min, so as to obtain a crude product B.
The crude product B was dissolved in 200g of ethyl acetate, and then filtered and concentrated to give a concentrated solution C.
And (3) rotationally evaporating the obtained concentrated solution C at 60 ℃ until no liquid exists, and rotationally evaporating the concentrated solution C at 180 ℃ for 6 hours to obtain the high-purity lithium bisoxalato borate.
Performance testing
The lithium bisoxalato borate prepared in examples 1 to 8 and comparative examples 1 to 5 were tested for yield, moisture and purity, and the specific results are shown in table 1. XRD patterns of lithium bisoxalato borate in examples 1 to 8 and comparative examples 1 to 5 were measured, and are specifically shown in FIG. 1.
TABLE 1 results of yield, moisture and purity tests for lithium bisoxalato borate
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The preparation method of the lithium bisoxalato borate is characterized by comprising the following steps:
1) Mixing a lithium source, a boron source and an oxalic acid compound, and performing ball milling to obtain a mixed material;
2) Spreading the mixed material in a microwave hot-pressing device for microwave hot-pressing reaction to obtain lithium bisoxalato borate;
the pressure of the microwave hot-pressing reaction is 0.1-20 Mpa;
the time of the microwave hot-pressing reaction is 5-100 min.
2. The method according to claim 1, wherein the molar ratio of the lithium source, boric acid and oxalic acid compound is 0.8 to 1.1:0.8 to 1.2:2.0 to 2.3.
3. The preparation method according to claim 1, wherein the ball milling time is 25-35 min; the rotating speed is 90-110 r/min.
4. The method according to claim 1, wherein the microwave power of the microwave hot-pressing reaction is 100-500 w.
5. The method according to claim 1, wherein the temperature of the microwave hot-pressing reaction is 100 to 240 ℃.
6. The method of claim 1, wherein the microwave hot pressing apparatus comprises a pressing upper platen, a pressing lower platen, and a microwave emitter plate; a trough is arranged in the tabletting lower pressing plate;
the microwave transmitting plate is arranged at the lower part of the pressing plate upper pressing plate, is integrated with the pressing plate upper pressing plate, and is matched with the pressing plate lower pressing plate trough.
7. The method according to claim 6, wherein the pressing rate of the upper pressing plate and the lower pressing plate of the microwave hot pressing device is 0.1-100 mm/s when the microwave hot pressing reaction is performed.
8. The method of claim 1, further comprising dissolving the lithium bisoxalato borate in an organic solvent, filtering, concentrating, and drying.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2617559Y (en) * | 2003-05-19 | 2004-05-26 | 电子科技大学 | Microwave hot press shaper |
| CN1725535A (en) * | 2005-07-08 | 2006-01-25 | 长沙丰日电气集团有限公司 | Hydrogen air fuel battery MEA microwave hot-press method and device |
| CN1846977A (en) * | 2005-12-09 | 2006-10-18 | 孙辰豪 | Microwave themal compression machine bench |
| CN101397305A (en) * | 2007-09-30 | 2009-04-01 | 比亚迪股份有限公司 | Method for preparing bisoxalatoborate |
| JP2011246305A (en) * | 2010-05-26 | 2011-12-08 | Hiroshima Univ | Method for producing powder by solid phase reaction |
| CN104477892A (en) * | 2014-12-12 | 2015-04-01 | 盐城市新能源化学储能与动力电源研究中心 | Preparation method of flake graphene and flake graphene device prepared by same |
| CN109232629A (en) * | 2018-11-28 | 2019-01-18 | 湖南科霸汽车动力电池有限责任公司 | The preparation method of di-oxalate lithium borate |
| KR20190096154A (en) * | 2018-02-08 | 2019-08-19 | 리켐주식회사 | Synthetic Method of Lithium bisoxalatoborate |
| CN112427638A (en) * | 2020-12-04 | 2021-03-02 | 湖南伊澍工业技术有限公司 | Oscillating hot-pressing sintering furnace with pressurizing auxiliary structure |
| WO2021146815A1 (en) * | 2020-01-24 | 2021-07-29 | HYDRO-QUéBEC | Polymers based on ionic monomers, compositions comprising same, methods for manufacturing same, and use thereof in electrochemical applications |
| WO2021256888A1 (en) * | 2020-06-18 | 2021-12-23 | 이피캠텍 주식회사 | Method for preparing highly pure lithium bisoxalatoborate, and secondary battery non-aqueous electrolyte using same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8927757B2 (en) * | 2010-01-18 | 2015-01-06 | Merck Patent Gmbh | Process for the preparation of perfluoroalkylcyano- or perfluoroalkylcyanofluoroborates |
| FR3000956B1 (en) * | 2013-01-17 | 2017-12-08 | Commissariat Energie Atomique | PROCESS FOR THE SYNTHESIS OF LIM1-X-Y-ZNYQZFEXPO4 COMPOUND AND ITS USE AS ELECTRODE MATERIAL FOR LITHIUM ACCUMULATOR |
| CN110492174A (en) * | 2019-08-20 | 2019-11-22 | 浙江地坤键新能源科技有限公司 | A kind of solid electrolyte of alkali ion movement and its preparation method and application |
-
2021
- 2021-12-28 CN CN202111625523.1A patent/CN114181240B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2617559Y (en) * | 2003-05-19 | 2004-05-26 | 电子科技大学 | Microwave hot press shaper |
| CN1725535A (en) * | 2005-07-08 | 2006-01-25 | 长沙丰日电气集团有限公司 | Hydrogen air fuel battery MEA microwave hot-press method and device |
| CN1846977A (en) * | 2005-12-09 | 2006-10-18 | 孙辰豪 | Microwave themal compression machine bench |
| CN101397305A (en) * | 2007-09-30 | 2009-04-01 | 比亚迪股份有限公司 | Method for preparing bisoxalatoborate |
| JP2011246305A (en) * | 2010-05-26 | 2011-12-08 | Hiroshima Univ | Method for producing powder by solid phase reaction |
| CN104477892A (en) * | 2014-12-12 | 2015-04-01 | 盐城市新能源化学储能与动力电源研究中心 | Preparation method of flake graphene and flake graphene device prepared by same |
| KR20190096154A (en) * | 2018-02-08 | 2019-08-19 | 리켐주식회사 | Synthetic Method of Lithium bisoxalatoborate |
| CN109232629A (en) * | 2018-11-28 | 2019-01-18 | 湖南科霸汽车动力电池有限责任公司 | The preparation method of di-oxalate lithium borate |
| WO2021146815A1 (en) * | 2020-01-24 | 2021-07-29 | HYDRO-QUéBEC | Polymers based on ionic monomers, compositions comprising same, methods for manufacturing same, and use thereof in electrochemical applications |
| WO2021256888A1 (en) * | 2020-06-18 | 2021-12-23 | 이피캠텍 주식회사 | Method for preparing highly pure lithium bisoxalatoborate, and secondary battery non-aqueous electrolyte using same |
| CN112427638A (en) * | 2020-12-04 | 2021-03-02 | 湖南伊澍工业技术有限公司 | Oscillating hot-pressing sintering furnace with pressurizing auxiliary structure |
Non-Patent Citations (2)
| Title |
|---|
| Microwave curing of carbon fiber/bismaleimide composite laminates: Material characterization and hot pressing pretreatment;Xu, XH等;MATERIALS & DESIGN;第97卷;316-323 * |
| 双草酸硼酸锂在锂离子电池中的应用研究进展;任铁强;乔庆东;孙悦;李琪;;化学通报(第12期);1081-1085 * |
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