CN111943985A - Synthetic method of oxalate lithium phosphate compound - Google Patents

Synthetic method of oxalate lithium phosphate compound Download PDF

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CN111943985A
CN111943985A CN201910412342.7A CN201910412342A CN111943985A CN 111943985 A CN111943985 A CN 111943985A CN 201910412342 A CN201910412342 A CN 201910412342A CN 111943985 A CN111943985 A CN 111943985A
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lithium
oxalate
phosphate
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贺伟
董剑
文娟·刘·麦蒂斯
熊亚丽
郑宣鸣
张志刚
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Weihong Advanced Materials Co
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Microvast Power Systems Huzhou Co Ltd
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Abstract

The invention discloses a synthesis method of lithium oxalate phosphate compounds with low reaction temperature and high product yield. Chloride ions are not introduced in the synthesis process, the purity can reach 99%, and the product can be directly used as an electrolyte additive without further treatment.

Description

Synthetic method of oxalate lithium phosphate compound
Technical Field
The invention relates to a method for synthesizing oxalate lithium phosphate compounds.
Background
Lithium oxalate phosphate compounds are generally used as additives for nonaqueous electrolyte batteries such as lithium ion batteries and lithium ion capacitors. The commonly used lithium oxalato phosphate-based compound includes lithium difluorobis (oxalato) phosphate, and Japanese patent publication No. JP2003137890A discloses a method for producing lithium difluorobis (oxalato) phosphate by dissolving lithium hexafluorophosphate in an organic solvent containing SiCl4The reaction assistant (c) is reacted. However, the manufacturing method thereofThe by-products produced in the process are HCl and silicon tetrafluoride or silicon tetrachloride, which adversely affect the performance of the nonaqueous electrolyte battery. In addition, the large amount of heat generated during the reaction and the strong corrosiveness of HCl also make the synthesis difficult to industrialize.
Disclosure of Invention
The invention provides a method for synthesizing oxalate lithium phosphate compounds, which comprises the following steps: ammonium hexafluorophosphate or amine salt shown in formula (2), silicon-based oxalate shown in formula (3) and lithium hydride are mixed in a non-aqueous solvent to react to obtain an oxalate lithium phosphate compound shown in formula (1);
Figure BDA0002063222230000011
wherein n is1Selected from 0, 2, 4; n is2Selected from 1,2, 3;
Figure BDA0002063222230000012
Figure BDA0002063222230000021
wherein R is1、R2And R3Each independently selected from hydrogen and C1-C6Alkyl of (C)2-C6Alkenyl or C6-C10Aryl of (a); r1、R2、R3Each substituent is the same or different; r1、R2、R3Not hydrogen at the same time;
Figure BDA0002063222230000022
wherein R is4、R5、R6、R7、R8And R9Each independently selected from hydrogen and C1-C6Alkyl radical, C2-C6Alkenyl or C6-C10Aryl of (a); r4、R5、R6、R7、R8And R9Each substituent may be the same or different.
In the present invention, when n is1Is selected from 0, n23, the obtained lithium oxalate phosphate salt compound is lithium tris (oxalate) phosphate; when n is1When selected from 2, n22, the obtained lithium oxalate phosphate compound is lithium difluoro (bis-oxalate) phosphate; when n is1Is selected from 4, n2Selected from 1, and the obtained lithium oxalate phosphate salt compound is lithium tetrafluoro (oxalate) phosphate.
As an implementation mode, ammonium hexafluorophosphate or amine salt shown in formula (2) and silicon-based oxalate shown in formula (3) are mixed in a non-aqueous solvent to carry out a primary reaction, lithium hydride is added after the primary reaction to carry out a secondary reaction, and the oxalate lithium phosphate compound shown in formula (1) is obtained after the secondary reaction; the intermediate product obtained after the preliminary reaction is amine salt or ammonium oxalate ammonium phosphate shown in a formula (4);
Figure BDA0002063222230000023
the invention can remove the solvent after selective reaction to obtain the lithium oxalate phosphate compound shown in the formula (1).
The R is1、R2、R3、R4、R5、R6、R7、R8And R9Each independently selected from hydrogen, methyl, ethyl, vinyl or phenyl.
The lithium oxalate phosphate compound includes at least one of lithium tetrafluoro (oxalate) phosphate (litfip), lithium difluoro (bis-oxalate) phosphate (lidbop), and lithium tris (oxalate) phosphate (LiTOP).
The molar ratio of ammonium hexafluorophosphate or amine salt to silicon-based oxalate is 1.00: 0.95-1.00: 8.10; as an embodiment, the molar ratio of ammonium hexafluorophosphate or amine salt to silicon based oxalate is 1.00: 0.95-1.00: 5.10; as an embodiment, the molar ratio of ammonium hexafluorophosphate or amine salt to silicon based oxalate is 1.00: 0.95-1.00: 3.20.
the target product of the invention is lithium oxalate phosphate salt compound, including at least one of lithium tetrafluoro (oxalate) phosphate (litfip), lithium difluoro (bis-oxalate) phosphate (lidbop) and lithium tris (oxalate) phosphate (LiTOP). The present invention can prepare high purity LiDFBOP, high purity LiTFOP, high purity LiTOP or a mixture thereof by adjusting the molar ratio of ammonium hexafluorophosphate or silicon based oxalate of an amine salt. The molar ratio of ammonium hexafluorophosphate or amine salt to silicon-based oxalate is 1.00: 0.95-1.00: 1.20, the final target product is high-purity LiTFOP. The molar ratio of ammonium hexafluorophosphate or amine salt to silicon-based oxalate is 1.00: 2.05-1.00: at 2.20, the final target product was LiDFBOP of high purity. The molar ratio of ammonium hexafluorophosphate or amine salt to silicon-based oxalate is 1.00: 3.05-1.00: at 3.20, the final target product is high purity LiTOP. The molar ratio of ammonium hexafluorophosphate or amine salt to silicon-based oxalate is 1.00: 0.95-1.00: 3.20, and the final product is a mixture except the proportion range; for example, the molar ratio of ammonium hexafluorophosphate or amine salt to silicon based oxalate is 1.00: 1.20-1.00: within 2.05 and not including the boundary values, the final target product is a mixture of the LiDFBOP and the LiTFOP; and if the molar ratio of ammonium hexafluorophosphate or amine salt to silicon-based oxalate is 1.00: 2.20-1.00: within 3.05 and not including the boundary values, the final target product was a mixture of lidbop and LiTOP. The molar ratio of ammonium hexafluorophosphate or amine salt to silicon-based oxalate is 1.00: 3.20-1.00: within 8.10 and not including the boundary values, the final product is a mixture of LiTOP and silicon-based oxalate.
The invention can prepare mixed or high-purity single or lithium oxalate phosphate by adjusting the molar ratio of ammonium hexafluorophosphate or amine salt to silicon-based oxalate, namely the molar percentage of the single or mixed lithium oxalate phosphate in the product reaches 95.2-99.0 percent, and further 97.0-99.0 percent. For example, when the molar ratio of ammonium hexafluorophosphate or amine salt to silicon based oxalate is 1.00: 0.95-1.00: 1.20, according to the preparation method of the invention, the LiTFOP with the mole percentage of 95.2-99.0% can be prepared. Further, by subsequent water removal or drying treatment of the present invention, or by selecting the reaction conditions of the present invention such as temperature and time for the reaction, the molar percentage of the mixed or high-purity single lithium oxalate phosphate salt prepared by the present invention can be 95.2% to 100%, further 97.0% to 100%.
In one embodiment, the molar ratio of ammonium hexafluorophosphate or amine salt to lithium hydride is 1.00: 0.95-1.00: 1.50; in one embodiment, the molar ratio of ammonium hexafluorophosphate or amine salt to lithium hydride is 1.00: 0.95-1.00: 1.20.
the proportion range can ensure that the raw materials are fully reacted to obtain the high-purity lithium salt which can be directly used as the nonaqueous electrolyte additive, and if the amount of lithium hydride is too small, the raw materials are not fully reacted to obtain the high-purity lithium salt; if the amount of lithium hydride is too large, the residual amount of lithium hydride increases, which makes the post-treatment difficult and increases the cost.
In one embodiment, the nonaqueous solvent is at least one selected from the group consisting of cyclic carbonates, chain nitriles, cyclic esters, chain esters, and halogenated solvents.
In one embodiment, the non-aqueous solvent is at least one selected from the group consisting of propylene carbonate, ethylene carbonate, butylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, acetonitrile, propionitrile, butyrolactone, valerolactone, ethyl acetate, ethyl propionate, methylene chloride, and 1, 2-dichloroethane. The nonaqueous solvent used in the present invention may be used alone, or two or more kinds thereof may be mixed in any combination and in any ratio according to the use. These solvents are preferably dehydrated solvents. The method of dehydration in the present invention is not particularly limited, and includes, but is not limited to, a method of adsorbing water by synthetic zeolite or the like.
As an embodiment, the reaction temperature of the primary reaction and the secondary reaction is-20 ℃ to 100 ℃; as an embodiment, the reaction temperature of the primary reaction and the secondary reaction is-20 ℃ to 25 ℃; in one embodiment, the temperature is 25 ℃ to 50 ℃; in one embodiment, the reaction temperature of the primary reaction and the secondary reaction is 50 ℃ to 100 ℃.
When the reaction temperature of the initial reaction in the synthesis method is 50-100 ℃, only byproduct fluoro trialkyl silane in the reaction process can be completely removed, and high-purity lithium salt can be obtained. When the reaction temperature of the initial reaction is reduced to less than 50 ℃, the rate of removing the byproduct fluoro-trialkylsilane is greatly reduced. When the reaction temperature of the initial reaction exceeds 100 ℃, the non-aqueous solvent is decomposed, and the performance of the electrolyte is affected.
As an embodiment, the reaction time of the primary reaction and the secondary reaction is 1-24 h; as an embodiment, the reaction time of the primary reaction and the secondary reaction is 1-12 h; as an embodiment, the reaction time of the primary reaction and the secondary reaction is 12-24 h.
In one embodiment, the yield of the lithium oxalate phosphate compound is 70% to 94%. The yield of the invention refers to the ratio of the actual yield to the theoretical yield of the lithium oxalate phosphate compound.
The synergistic effect of the reaction temperature and the reaction time can improve the yield of the lithium oxalate phosphate compound prepared by the invention. Considering the temperature alone, if the reaction temperature is too high, the product may be decomposed, and the yield is reduced; if the reaction temperature is too low, the reaction may be insufficient, resulting in a decrease in yield. Considering the reaction time alone, if the reaction time is too long, the decomposition of the product may be caused, and the yield is reduced; if the reaction time is too short, the reaction may be insufficient, resulting in a decrease in yield. The reaction time and the reaction temperature are matched with each other, so that the technical effect of the invention can be achieved.
As an embodiment, the reaction is carried out in an inert atmosphere; in one embodiment, the inert atmosphere is nitrogen and/or argon.
The invention also aims to provide an oxalate lithium phosphate compound which is prepared by adopting the synthesis method of the oxalate lithium phosphate compound.
Another object of the present invention is to provide an electrolyte solution containing the lithium oxalate phosphate compound.
The invention also aims to provide a lithium ion battery which comprises the electrolyte.
The invention has the beneficial effects that:
1. the preparation method has the advantages of low cost and easy obtainment of raw materials, simple reaction operation, capability of synthesizing different lithium oxalate phosphate compounds by changing the reaction charging proportion and high reaction yield.
2. The preparation method of the invention does not introduce chloride ions in the synthesis process, the byproduct fluoro trialkyl silane can be removed under the synthesis condition or in the drying process of removing the solvent at the later stage, the purity of the target product can reach 99 percent, and the product can be directly used as an electrolyte additive without further treatment.
Detailed Description
The following specific examples describe the present invention in detail, however, the present invention is not limited to the following examples.
Example 1:
0.124mol of ammonium hexafluorophosphate, 0.254mol of bistrimethylsilyl oxalate, 0.150mol of lithium hydride and anhydrous diethyl carbonate were added to a 500ml round bottom flask in a glove box and reacted at 80 ℃ for 24h until no more gas was generated. The solvent was then removed to give a white solid in 94% yield. Nuclear magnetic test results show that lidbop: the ratio of LiTFOP was 72:1 and the mole percentage of litbop was 98.6%.
Example 2:
0.124mol of ammonium hexafluorophosphate and anhydrous diethyl carbonate, and 0.273mol of bistrimethylsilyl oxalate were added to a 500ml round bottom flask in a glove box and reacted at 100 ℃ for 1h until no more gas was generated. 0.118mol of lithium hydride is added for further reaction, and the reaction is carried out for 1h at 100 ℃. The solvent was then removed to give a white solid in 89% yield. Nuclear magnetic test results show that lidbop: the ratio of LiTFOP was 20:1 and the mole percentage of LiTFOP was 95.2%.
Example 3:
the same as example 2 except that ammonium hexafluorophosphate and bistrimethylsilyl oxalate were added in amounts of 0.124mol and 0.254mol, respectively, and the product yield was 88%, the nuclear magnetic testing results showed that LiDFBOP: the ratio of LiTFOP was 72:1 and the mole percentage of litbop was 98.6%.
Example 4:
the same as example 2 except that ammonium hexafluorophosphate and bistrimethylsilyl oxalate were added in amounts of 0.124mol and 0.262mol, respectively, and the product yield was 89%, the nuclear magnetic testing results showed that LiDFBOP: the ratio of LiTFOP was 55:1 and the mole percentage of litbop was 98.2%.
Example 5:
0.124mol of ammonium hexafluorophosphate and anhydrous dimethyl carbonate, and 0.14mol of bistrimethylsilyl oxalate were added to a 500ml round bottom flask in a glove box and reacted at 20 ℃ for 12h until no more gas was generated. 0.124mol of lithium hydride is added for further reaction, and the reaction is carried out for 12h at 20 ℃. The solvent was then removed to give a white solid in 80% yield. Nuclear magnetic test results show that lidbop: the ratio of litfo was 1:66, and the mole percentage of litfo was 98.5%.
Example 6:
the same as example 5 except that ammonium hexafluorophosphate and bistrimethylsilyl oxalate were added in amounts of 0.124mol and 0.118mol, respectively, and the product yield was 76%, the nuclear magnetic test results showed that LiDFBOP: the ratio of litfo was 1:37, and the mole percentage of litfo was 97.4%.
Example 7:
the same as example 5 except that ammonium hexafluorophosphate and bistrimethylsilyl oxalate were added in amounts of 0.124mol and 0.149mol, respectively, and the product yield was 82%, the nuclear magnetic testing results showed that LiDFBOP: the ratio of litfo was 1:24, and the mole percentage of litfo was 96.0%.
Example 8:
0.124mol of ammonium hexafluorophosphate and ethyl methyl carbonate anhydrous, and 0.396mol of bistrimethylsilyl oxalate were added to a 500ml round bottom flask in a glove box and reacted at 60 ℃ for 6h until no more gas was generated. 0.15mol of lithium hydride is added for further reaction, and the reaction is carried out for 6h at 60 ℃. The solvent was then removed to give a white solid in 83% yield. Nuclear magnetic test results show that lidbop: the ratio of LiTOP was 1:100, the mole percentage of LiTOP was 99.0%.
Example 9:
the same as example 8 except that ammonium hexafluorophosphate and bistrimethylsilyl oxalate were added in amounts of 0.124mol and 0.384mol, respectively, and the product yield was 80%, nuclear magnetic resonance test results showed that LiDFBOP: the ratio of lipo was 1:41, the mole percentage of lipo was 97.6%.
Example 10:
the same as example 8 except that ammonium hexafluorophosphate and bistrimethylsilyl oxalate were added in amounts of 0.124mol and 0.378mol, respectively, and the product yield was 73%, the nuclear magnetic testing results showed that LiDFBOP: the ratio of LiTOP was 1:20, the mole percentage of LiTOP was 95.2%.
Example 11:
the same as example 8 except that ammonium hexafluorophosphate and bistrimethylsilyl oxalate were added in amounts of 0.124mol and 0.632mol, respectively, and the product yield was 75%, the nuclear magnetic testing results showed that LiDFBOP: the ratio of LiTOP was 1:80, the mole percentage of LiTOP was 98.8%.
Example 12:
the same as example 8 except that ammonium hexafluorophosphate and bistrimethylsilyl oxalate were added in amounts of 0.124mol and 0.992mol, respectively, and the product yield was 76%, the nuclear magnetic testing results showed that LiDFBOP: the ratio of lipo was 1:90, and the mole percentage of lipo was 99.0%.
Example 13:
0.124mol of ammonium hexafluorophosphate and anhydrous ethyl acetate, and 0.186mol of bistrimethylsilyl oxalate were added to a 500ml round bottom flask in a glove box and reacted at 50 ℃ for 3 hours until no more gas was generated. 0.15mol of lithium hydride is added for further reaction, and the reaction is carried out for 3 hours at 50 ℃. The solvent was then removed to give a white solid in 70% yield. Nuclear magnetic test results show that lidbop: the ratio of litfo was 2:4 and the mole percentage of litfo was 66.7%.
Example 14:
0.124mol of ammonium hexafluorophosphate and diethyl carbonate anhydrous, and 0.31mol of bis tri-n-butylsilyl oxalate were added to a 500ml round bottom flask in a glove box and reacted at 90 ℃ for 6 hours until no more gas was generated. 0.15mol of lithium hydride is added for further reaction, and the reaction is carried out for 6h at 90 ℃. The solvent was then removed to give a white solid in 78% yield. Nuclear magnetic test results show that lidbop: the ratio of lipo was 9:5 and the mole percentage of the lipobop was 64.3%.
Example 15:
0.124mol of ammonium hexafluorophosphate and diethyl carbonate anhydrous, and 0.375mol of bis (diethylvinyl) silyl oxalate were added to a 500ml round bottom flask in a glove box and reacted at 60 ℃ for 8h until no more gas was generated. 0.15mol of lithium hydride is added for further reaction, and the reaction is carried out for 8h at 60 ℃. The solvent was then removed to give a white solid in 91% yield. Nuclear magnetic test results show that lidbop: the ratio of lipo was 11:1 and the mole percentage of the lipobop was 91.7%.
Example 16:
same as in example 14, except that ammonium hexafluorophosphate was replaced with NH (Et)3)PF6The yield was 75%. Nuclear magnetic test results show that lidbop: the ratio of lipo was 9:5 and the mole percentage of the lipobop was 64.3%.
Example 17:
same as example 15, except that ammonium hexafluorophosphate was replaced with NH (Me)3)PF6The yield was 90%. Nuclear magnetic test results show that lidbop: the ratio of LiTOP was 1:10 with the mole percentage of LiTOP being 90.9%.

Claims (15)

1. A method for synthesizing oxalate lithium phosphate compounds comprises the following steps: ammonium hexafluorophosphate or amine salt shown in formula (2), silicon-based oxalate shown in formula (3) and lithium hydride are mixed in a non-aqueous solvent to react to obtain an oxalate lithium phosphate compound shown in formula (1);
Figure FDA0002063222220000011
wherein n is1Selected from 0, 2, 4; n is2Selected from 1,2, 3;
Figure FDA0002063222220000012
wherein R is1、R2And R3Each independently selected from hydrogen and C1-C6Alkyl of (C)2-C6Alkenyl or C6-C10Aryl of (a); r1、R2、R3Each substituent is the same or different; r1、R2、R3Not hydrogen at the same time;
Figure FDA0002063222220000013
wherein R is4、R5、R6、R7、R8And R9Each independently selected from hydrogen and C1-C6Alkyl radical, C2-C6Alkenyl or C6-C10Aryl of (a); r4、R5、R6、R7、R8And R9Each substituent may be the same or different.
2. The method for synthesizing lithium oxalato phosphate salt compounds as claimed in claim 1, wherein ammonium hexafluorophosphate or amine salt represented by formula (2) and silicon-based oxalate represented by formula (3) are mixed in a non-aqueous solvent to perform a preliminary reaction, lithium hydride is added after the preliminary reaction to perform a secondary reaction, and the lithium oxalato phosphate salt compounds represented by formula (1) are obtained after the secondary reaction.
3. The method for synthesizing a lithium oxalate phosphate compound according to claim 1 or 2, wherein the solvent is removed after the reaction to obtain a lithium oxalate phosphate compound represented by the formula (1).
4. The method for synthesizing a lithium oxalate phosphate compound according to claim 1, wherein R is1、R2、R3、R4、R5、R6、R7、R8And R9Each independently selected from hydrogen, methyl, ethyl, vinyl or phenyl.
5. The method for synthesizing a lithium oxalate phosphate compound according to claim 1, wherein the lithium oxalate phosphate compound includes at least one of lithium tetrafluoro (oxalate) phosphate, lithium difluoro (bis-oxalate) phosphate, and lithium tris (oxalate) phosphate.
6. The method for synthesizing lithium oxalate phosphate salt-based compound according to claim 1, wherein the molar ratio of ammonium hexafluorophosphate or amine salt to silicon-based oxalate is 1.00: 0.95-1.00: 8.10.
7. the method for synthesizing a lithium oxalate phosphate salt-based compound according to claim 1, wherein the molar ratio of ammonium hexafluorophosphate or an amine salt to lithium hydride is 1.00: 0.95-1.00: 1.50.
8. the method for synthesizing a lithium oxalate phosphate salt-based compound according to claim 1, wherein the nonaqueous solvent is at least one selected from the group consisting of cyclic carbonates, chain nitriles, cyclic esters, chain esters, and halogenated solvents.
9. The method according to claim 8, wherein the nonaqueous solvent is at least one selected from the group consisting of propylene carbonate, ethylene carbonate, butylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, acetonitrile, propionitrile, butyrolactone, valerolactone, ethyl acetate, ethyl propionate, methylene chloride, and 1, 2-dichloroethane.
10. The method for synthesizing a lithium oxalate phosphate compound according to claim 2, wherein the reaction temperature for both the preliminary reaction and the secondary reaction is-20 ℃ to 100 ℃.
11. The method according to claim 10, wherein the preliminary reaction temperature is 50 ℃ to 100 ℃.
12. The method for synthesizing a lithium oxalate phosphate compound according to claim 1, wherein the reaction is carried out in an inert atmosphere; the inert atmosphere is nitrogen and/or argon.
13. A lithium oxalato phosphate salt compound, which is prepared by the method for synthesizing the lithium oxalato phosphate salt compound as claimed in claim 1.
14. An electrolytic solution comprising the lithium oxalate phosphate salt compound according to claim 13.
15. A lithium ion battery comprising the electrolyte of claim 14.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115583974A (en) * 2022-01-13 2023-01-10 安徽新宸新材料有限公司 Preparation method of lithium difluorobis (oxalate) phosphate

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1361787A (en) * 1999-07-22 2002-07-31 坎梅陶尔股份有限公司 Tris (oxalato) phosphates, method for their preparation and their use
CN102216311A (en) * 2008-12-16 2011-10-12 中央硝子株式会社 Method for producing lithium difluorobis(oxalato)phosphate solution
CN104334566A (en) * 2012-05-30 2015-02-04 中央硝子株式会社 Method for producing tetrafluoro(oxalate)phosphate solution
CN104334564A (en) * 2012-05-30 2015-02-04 中央硝子株式会社 Purified metal complex having oxalic acid as ligand, and method for producing purified solution of said metal complex in non-aqueous solvent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1361787A (en) * 1999-07-22 2002-07-31 坎梅陶尔股份有限公司 Tris (oxalato) phosphates, method for their preparation and their use
CN102216311A (en) * 2008-12-16 2011-10-12 中央硝子株式会社 Method for producing lithium difluorobis(oxalato)phosphate solution
CN104334566A (en) * 2012-05-30 2015-02-04 中央硝子株式会社 Method for producing tetrafluoro(oxalate)phosphate solution
CN104334564A (en) * 2012-05-30 2015-02-04 中央硝子株式会社 Purified metal complex having oxalic acid as ligand, and method for producing purified solution of said metal complex in non-aqueous solvent

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115583974A (en) * 2022-01-13 2023-01-10 安徽新宸新材料有限公司 Preparation method of lithium difluorobis (oxalate) phosphate
CN115583974B (en) * 2022-01-13 2023-09-05 安徽新宸新材料有限公司 Preparation method of difluoro lithium bisoxalato phosphate

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