CN102766151A - Method for purifying lithium bis(oxalate)borate - Google Patents
Method for purifying lithium bis(oxalate)borate Download PDFInfo
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- CN102766151A CN102766151A CN2011102398274A CN201110239827A CN102766151A CN 102766151 A CN102766151 A CN 102766151A CN 2011102398274 A CN2011102398274 A CN 2011102398274A CN 201110239827 A CN201110239827 A CN 201110239827A CN 102766151 A CN102766151 A CN 102766151A
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Abstract
The invention provides a method for purifying lithium bis(oxalate)borate, comprising the following steps of: dissolving a lithium bis(oxalate)borate crude product in an aprotic solvent, carrying out molecular sieve drying, filtering, carrying out evaporative concentration, carrying out thickening crystallization or mixed solvent crystallization, and repeating the steps to obtain high-purity lithium bis(oxalate)borate. C13-NMR spectrogram of the purified lithium bis(oxalate)borate is a single peak and its peak appearance location is 158.6 ppm. B11-NMR spectrogram is a single peak and its peak appearance location is 7.37 ppm. The content of metal impurity ions is determined by ICP. Contents of iron, chromium, sodium and nickel are respectively lower than 9 ppm, 1.1 ppm, 5 ppm and 0.4 ppm. The quality of the product accords with requirements of an electrolyte for lithium ion cells, and simultaneously the product is rapidly dissolved in the electrolyte. The purification technology provided by the invention is simple and easy to operate, and is suitable for industrial batch production.
Description
Technical field
The invention belongs to chemical field, relate to a kind of dioxalate group lithium borate (LiBOB) method of purification that can be used as lithium ion battery electrolyte.
Background technology
As the important component part of lithium ion battery, ionogen is most important for the lithium ion battery Effect on Performance.The electrolytical working mechanism that is determining battery to a great extent that is chosen in affects specific energy, security, cycle performance, storge quality and the cost etc. of battery.At present, the ionogen of commercial lithium ion battery use is mainly LiFP
6, its poor heat stability, to moisture-sensitive, facile hydrolysis, and low-temperature conductivity is lower.
In the research of novel organic electrolyte lithium salts, the of a great variety and environmental friendliness of novel boric acid lithium salts more and more causes people's attention in recent years.LiBOB most possibly substitutes LiPF
6Lithium salts.Dioxalate group lithium borate (LiBOB) thermostability is high, and is environmentally friendly, has excellent cycle performance under electrochemical window and the high temperature of broad.LiBOB has Ni-based good with manganese-based anode material flexibility; Stable to graphite cathode in the basic electrolytic solution of propylene carbonate (PC); Can prevent graphite and PC solvent common embedding and graphite cathode advantage such as peel off, widen the temperature application range of lithium ion battery greatly.
Mainly be to adopt oxalic acid (or barkite, oxalate) to be raw material in the existing dioxalate group lithium borate study on the synthesis, prepare LiBOB for raw material with boric acid (or boron oxide) and Lithium Hydroxide MonoHydrate (or Quilonum Retard).A kind of method is the solid phase method reaction, and direct reaction generates dioxalate group lithium borate.Another kind method is to adopt liquid phase method, and reaction generates dioxalate group lithium borate under solvent condition.Lithium ion battery has strict requirement to electrolytical quality.Usually directly the synthetic product can not directly use as lithium ion battery electrolyte because impurity and moisture content are higher.Therefore the LiBOB product must pass through purification step to lower foreign matter content.
Obtain the higher characteristics of the thick product moisture content of LiBOB to the liquid phase reaction method, patent CN200610105305 provides the method for purification of a kind of LiBOB.Earlier thick product is dissolved in polar aprotic solvent dry, that heavily steaming is handled, treats saturated after-filtration, evaporation concentration.Then with liquid concentrator in-10 ~-40 ℃ freezing 1 ~ 5 hour down, and place vacuum drying oven dry the solid matter, obtain the LiBOB of purifying.This method complex equipments, energy consumption is big.Patent CN200910213584 provides the method for purification of a kind of solid reaction process synthetic LiBOB.But shortcomings such as there is the raw materials mix lack of homogeneity in solid phase reaction method, and reaction process is difficult to accurate control, and level of response is low, therefore the method for purification based on solid reaction process synthetic LiBOB is not suitable for large-scale industrial production.These purification process; The product that uses acetonitrile, acetone, THF, ETHYLE ACETATE isopolarity aprotic solvent to obtain after the thick product of LiBOB is purified; Though foreign matter content reduces greatly, product still has the insolubles about 3% behind the purifying in electrolytic solution.In addition, the acetonitrile that uses in the purge process, ETHYLE ACETATE equal solvent are difficult to remove fully, and the residual solvent of trace can influence the quality of LiBOB, reduces the high temperature cyclic performance of lithium ion battery.
Summary of the invention
The object of the present invention is to provide a kind of method of purification of dioxalate group lithium borate, make the purity of LiBOB reach the requirement of lithium ion battery electrolyte quality, dissolution rate is fast simultaneously, and insolubles content is lower than 1%.
A kind of method of purification of dioxalate group lithium borate may further comprise the steps:
1, with the thick product of LiBOB under 30 ~ 100 ℃, be dissolved in through super-dry, heavily in the pretreated non-protonic solvent such as steaming, process saturated solution, and add the molecular sieve of handling through the super-dry pre-activated, insolubles is removed in filtration.
2, with one of methods such as evaporation concentration, condensing crystal, mixed solvent crystallization or its combination, obtain the dioxalate group lithium borate solid matter.
3, after the dioxalate group lithium borate solid matter that obtains can be used proper amount of solvent drip washing, place vacuum drying oven, 80 ℃ following dry 24～48 hours.
Non-protonic solvent involved in the present invention comprises methylcarbonate, diethyl carbonate, NSC 11801, Methyl ethyl carbonate, carbonic acid first propyl ester, propylene carbonate, gamma-butyrolactone, γ-Wu Neizhi, THF, N-Methyl pyrrolidone.Can use a kind of solvent wherein separately, also can use two or more solvent.
Obtain the dioxalate group lithium borate solid in order to one of following method or its combination:
A) will filtrate in vacuum, carry out evaporation concentration under 100 ~ 160 ℃ of conditions.The solvent amount of steaming is about 1/5 ~ 4/5 of an add-on.Methods such as the available filtration of filtrating after concentrating, suction filtration, spinning are carried out solid-liquid separation.
B) will filtrate in vacuum, carry out evaporation concentration under 100 ~ 160 ℃ of conditions, muddy to solution becomes.The solvent amount of steaming is about 1/20 ~ 1/2 of an add-on.Filtrating after concentrating was-40 ~ 10 ℃ of held 2 ~ 24 hours.The adularescent solid matter is separated out, and methods such as available filtration, suction filtration, spinning are carried out solid-liquid separation.
C) constantly stir down, filtrating is mixed with the poor solvent of dioxalate group lithium borate.The blending ratio of filtrating and poor solvent is 20:1 ~ 1:20.Mix back adularescent solid matter and separate out, methods such as available filtration, suction filtration, spinning are carried out solid-liquid separation.
The poor solvent of the dioxalate group lithium borate that the present invention relates to comprises aromatic hydrocarbons, ether, halohydrocarbon.Specifically comprise benzene,toluene,xylene; Dme, ether, methyl ethyl ether, sherwood oil; Phosgene, carbon trichloride, tetracol phenixin, ethylene dichloride, tetrachloroethane; Can use a kind of poor solvent wherein separately, also can use two or more poor solvent wherein.
Filter cake after the solid-liquid separation places vacuum drying oven after can using proper amount of solvent drip washing, and 80 ℃ following dry 24 ~ 48 hours.The white solid matter that obtains is the LiBOB product after the purification.
The drip washing solvent that the present invention relates to comprises aromatic hydrocarbons, ether, halohydrocarbon.Concrete is benzene,toluene,xylene; Dme, ether, methyl ethyl ether, sherwood oil; Phosgene, carbon trichloride, tetracol phenixin, ethylene dichloride, tetrachloroethane; Can use a kind of solvent wherein to carry out drip washing separately, also can use two or more solvent wherein to carry out drip washing.
Solvent after the solid-liquid separation through distillation, dry, heavily steam etc. handle after, but repeated application is in this purification process.
In order to obtain the dioxalate group lithium borate of required quality, can adopt method of the present invention to carry out purification repeatedly.
The product that the inventive method is purified detects through ir spectra, XRD and nuclear-magnetism method.The C of product behind the purifying
13-NMR spectrogram is unimodal, goes out peak position and is changed to 158.6 ppm, B
11-NMR spectrogram is unimodal, goes out peak position and is changed to 7.37 ppm.Insolubles content is lower than 1%.The metallic impurity ion content is measured by ICP.The content of iron, chromium, sodium, nickel is lower than 9 ppm respectively, 1.1 ppm, 5 ppm, 0.4 ppm.And the used non-protonic solvent of the present invention is the lithium-ion electrolyte common solvent, even there are trace solvent remnants also not influence the cycle performance of lithium ion battery in the LiBOB product.
The LiBOB product foreign matter content of method of purification gained of the present invention is low, and purity reaches the requirement of lithium ion battery electrolyte, and dissolution rate is fast, and insolubles content is lower than 1%.
Purifying technique of the present invention is simple, easily operation.And reusable after the solvent recuperation, be suitable for industrialized mass.
Embodiment
Embodiment 1:
Thick product of 100 g LiBOB and pretreated exsiccant molecular sieve are added in the pretreated Carbon Dioxide propylene of the 800 ml ester, be stirred to dissolution equilibrium.Filter, remove insolubles.Filtrating is carried out evaporation concentration in vacuum under 100 ~ 160 ℃ of conditions.The solvent amount of steaming is about 1/3 ~ 4/5 of an add-on.Filtered while hot.After the toluene wash of filter cake usefulness heat, place vacuum drying oven, 80 ℃ following dry 24 ~ 48 hours.The white solid matter that obtains is the LiBOB 45g after the purification.
Embodiment 2:
Thick product of 100 g LiBOB and pretreated exsiccant molecular sieve are added in the pretreated Carbon Dioxide vinyl acetate of 800 ml, be stirred to dissolution equilibrium.Filter, remove insolubles.Filtrating is carried out evaporation concentration in vacuum under 100 ~ 160 ℃ of conditions.The solvent amount of steaming is about 1/5 of an add-on.Liquid concentrator was-40 ~ 10 ℃ of held 2 ~ 24 hours.After the solid-liquid separation, after the toluene wash of filtrating with heat, place vacuum drying oven, 80 ℃ dry 24 ~ 48 hours down.The white solid matter that obtains is the LiBOB 17g after the purification.
Embodiment 3:
Thick product of 50 g LiBOB and pretreated exsiccant molecular sieve are added in the pretreated Carbon Dioxide propylene of the 400 ml ester, be stirred to dissolution equilibrium.Filter, remove insolubles.Filtrating is placed flask, constantly stir the toluene that adds 200 ~ 2000 ml down.There are a large amount of white crystals to separate out.Leave standstill moments later and to filter, after the toluene wash of filter cake with heat, place vacuum drying oven, 80 ℃ dry 24 ~ 48 hours down.The white solid matter that obtains is the LiBOB 37g after the purification.
Claims (8)
1. the method for purification of a dioxalate group lithium borate is characterized in that step is following:
(1) with the dioxalate group lithium borate bullion of required purification under 30 ~ 100 ℃, be dissolved in through super-dry, heavily in the pretreated non-protonic solvent such as steaming, and add the molecular sieve of handling through the super-dry pre-activated and carry out drying, insolubles is removed in filtration;
(2) with one of methods such as evaporation concentration, condensing crystal, mixed solvent crystallization or its combination, obtain the dioxalate group lithium borate solid matter;
(3) after the dioxalate group lithium borate solid matter that obtains can be used proper amount of solvent drip washing, place vacuum drying oven, 80 ℃ following dry 24 ~ 48 hours;
(4) dioxalate group lithium borate that obtains can repeat above step and repeatedly purify.
2. the method for purification of a kind of dioxalate group lithium borate as claimed in claim 1, it is characterized in that: wherein the described non-protonic solvent of step (1) comprises methylcarbonate, diethyl carbonate, NSC 11801, Methyl ethyl carbonate, carbonic acid first propyl ester, propylene carbonate, gamma-butyrolactone, γ-Wu Neizhi, THF, N-Methyl pyrrolidone etc.; Can use a kind of solvent wherein separately, also can use two or more mixed solvent.
3. the method for purification of a kind of dioxalate group lithium borate as claimed in claim 1 is characterized in that, wherein the described evaporating concentrating method of step (2) is: will filtrate in vacuum, and carry out evaporation concentration under 100 ~ 160 ℃ of conditions; The solvent amount of steaming is about 1/5 ~ 4/5 of an add-on; Methods such as the available filtration of filtrating after concentrating, suction filtration, spinning are carried out solid-liquid separation.
4. the method for purification of a kind of dioxalate group lithium borate as claimed in claim 1; It is characterized in that; Wherein the described condensation crystallization method of step (2) is: will filtrate in vacuum, carry out evaporation concentration under 100 ~ 160 ℃ of conditions, and muddy to solution becomes; Form supersaturated solution, the solvent amount of steaming is about 1/20 ~ 1/2 of an add-on; Filtrating after concentrating was-40 ~ 10 ℃ of held 2 ~ 24 hours, and the adularescent solid matter is separated out; Methods such as available filtration, suction filtration, spinning are carried out solid-liquid separation.
5. the method for purification of a kind of dioxalate group lithium borate as claimed in claim 1 is characterized in that, wherein the described mixed solvent crystallization method of step (2) is: constantly stir down, filtrating is mixed with the poor solvent of dioxalate group lithium borate; The blending ratio of filtrating and poor solvent is 20:1 ~ 1:20; Mix back adularescent solid matter and separate out, methods such as available filtration, suction filtration, spinning are carried out solid-liquid separation.
6. the method for purification of a kind of dioxalate group lithium borate described in claim 1 and 5, it is characterized in that: the poor solvent of described dioxalate group lithium borate comprises aromatic hydrocarbons, ether, halohydrocarbon.
7. the method for purification described in claim 5 and 6, it is characterized in that: the poor solvent of described dioxalate group lithium borate is a benzene,toluene,xylene; Dme, ether, methyl ethyl ether, sherwood oil; Phosgene, carbon trichloride, tetracol phenixin, ethylene dichloride, tetrachloroethane; Can use a kind of poor solvent wherein separately, also can use two or more poor solvent wherein.
8. the method for purification of a kind of dioxalate group lithium borate as claimed in claim 1 is characterized in that, wherein the described method of purification of step (3) is: the solvent that relates to drip washing is the poor solvent of dioxalate group lithium borate, comprises benzene,toluene,xylene; Dme, ether, methyl ethyl ether, sherwood oil; Phosgene, carbon trichloride, tetracol phenixin, ethylene dichloride, tetrachloroethane; Can use a kind of poor solvent wherein separately, also can use two or more poor solvent wherein.
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| CN2011102398274A CN102766151A (en) | 2011-05-05 | 2011-08-21 | Method for purifying lithium bis(oxalate)borate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053786A (en) * | 2018-09-18 | 2018-12-21 | 天津金牛电源材料有限责任公司 | A kind of preparation method of di-oxalate lithium borate |
| CN109503635A (en) * | 2018-12-06 | 2019-03-22 | 东营石大胜华新能源有限公司 | A kind of di-oxalate lithium borate purification process |
| CN111057079A (en) * | 2019-12-16 | 2020-04-24 | 江苏华盛锂电材料股份有限公司 | Purification method of lithium bis (oxalato) borate and lithium bis (oxalato) borate |
| CN111153918A (en) * | 2019-12-16 | 2020-05-15 | 山东石大胜华化工集团股份有限公司 | Preparation method of lithium bis (oxalato) borate |
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| CN1817888A (en) * | 2006-03-06 | 2006-08-16 | 北京科技大学 | Purification of duplex dicarboxyl-base lithium borate |
| CN100999529A (en) * | 2006-12-11 | 2007-07-18 | 中国科学院青海盐湖研究所 | Purifying process of biethyl diacid lithium borate |
| CN101033184A (en) * | 2006-03-10 | 2007-09-12 | 北京格林动力电源技术有限公司 | Method of preparing boron lithium dioxalate complex salt |
| CN101861323A (en) * | 2007-07-04 | 2010-10-13 | 凯密特尔有限责任公司 | Crystalline, completely soluble lithium bis(oxalato)borate (LiBOB) |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1817888A (en) * | 2006-03-06 | 2006-08-16 | 北京科技大学 | Purification of duplex dicarboxyl-base lithium borate |
| CN101033184A (en) * | 2006-03-10 | 2007-09-12 | 北京格林动力电源技术有限公司 | Method of preparing boron lithium dioxalate complex salt |
| CN100999529A (en) * | 2006-12-11 | 2007-07-18 | 中国科学院青海盐湖研究所 | Purifying process of biethyl diacid lithium borate |
| CN101861323A (en) * | 2007-07-04 | 2010-10-13 | 凯密特尔有限责任公司 | Crystalline, completely soluble lithium bis(oxalato)borate (LiBOB) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053786A (en) * | 2018-09-18 | 2018-12-21 | 天津金牛电源材料有限责任公司 | A kind of preparation method of di-oxalate lithium borate |
| CN109053786B (en) * | 2018-09-18 | 2021-06-15 | 天津金牛电源材料有限责任公司 | Preparation method of lithium bis (oxalato) borate |
| CN109503635A (en) * | 2018-12-06 | 2019-03-22 | 东营石大胜华新能源有限公司 | A kind of di-oxalate lithium borate purification process |
| CN111057079A (en) * | 2019-12-16 | 2020-04-24 | 江苏华盛锂电材料股份有限公司 | Purification method of lithium bis (oxalato) borate and lithium bis (oxalato) borate |
| CN111153918A (en) * | 2019-12-16 | 2020-05-15 | 山东石大胜华化工集团股份有限公司 | Preparation method of lithium bis (oxalato) borate |
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Application publication date: 20121107 |