CN100503617C - Purifying process of biethyl diacid lithium borate - Google Patents
Purifying process of biethyl diacid lithium borate Download PDFInfo
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- CN100503617C CN100503617C CNB2006101053054A CN200610105305A CN100503617C CN 100503617 C CN100503617 C CN 100503617C CN B2006101053054 A CNB2006101053054 A CN B2006101053054A CN 200610105305 A CN200610105305 A CN 200610105305A CN 100503617 C CN100503617 C CN 100503617C
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- libob
- lithium borate
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- biethyl diacid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The process of purifying LiBOB includes the following steps: dissolving LiBOB material with low LiBOB content and high water content in dried and re-distilling treated polar non-protonic solvent to form saturated solution, filtering and evaporating to concentrate; freezing at -10 deg.c to -40 deg.c for 1-5 hr; and vacuum drying to obtain purified LiBOB product. The purified LiBOB product, the infrared spectrum analysis and 13C and 11B nuclear magnetic resonance spectrum show, has total content of Li, B and oxalate ions greater than 99.30 wt%. After twice purifications, the product has water content as low as 0.0014 wt% and the contents of Na, K, Ca, Mg and Fe lower than 0.0020 wt%, 0.0010 wt%, 0.0010 wt%, 0.00040 wt% and 0.00080 wt% separately, and may be used as the lithium salt for lithium ion cell electrolyte.
Description
Technical field
The invention belongs to chemical field, relate to a kind of purification process that can be used as the biethyl diacid lithium borate (being called for short LiBOB) of lithium ion battery electrolyte.
Background technology
The used lithium salts of commercial lithium ion battery is mainly LiFP at present
6, but its thermostability is relatively poor, facile hydrolysis, and low-temperature conductivity is lower.Therefore, LiFP is compared in development
6Stability is better, not hydrolysis and be applicable to that the novel lithium salts of wide temperature range more becomes a research emphasis in current battery field.The novel lithium salts of research mainly concentrates on lithium-borate complexes and Trilithium phosphate title complex at present, and is among them, the most noticeable with biethyl diacid lithium borate (being called for short LiBOB) again.
LiBOB is as a kind of novel electrolytes lithium salts, and its thermostability and chemical stability are all better, and has the electrochemical window of high conductance and broad, even in pure PC solution, still can form stable SEI film in negative terminal surface; Its positive electrode material to manganese and iron system does not almost have dissolving and corrodes; In addition, it is not halogen-containing, is environmentally friendly lithium salts.
At present, the preparation method of relevant LiBOB mainly contains following two kinds:
1. compound (as the oxide compound or the boric acid ester of boric acid, the boron) reaction with the compound of lithium (as the alkoxide of lithium hydroxide, Quilonum Retard, lithium etc.), oxalic acid (or oxalate) and boron prepares (seeing DE 19829030).With lithium hydroxide, oxalic acid, boric acid are example, and its reaction equation is shown in (1):
(1)
2, with Li[B (OCH
3)
4] and (CH
3)
3SiOOCCSi (CH
3)
3In anhydrous acetonitrile, react to prepare and (see W.Xu, A.J.Shusterman.Electrochem.Solid-State Lett., 2001,4 (1): E1-E4).The equation of its reaction is shown in (2):
The ratio of the amount of substance of lithium ion, boron and oxalate can reach 1.0:0.99:2.0 in the method 2 gained LiBOB products; three kinds of ionic quality percentage compositions and also can reach 99.20% and (see Han Zhouxiang; Wei Jianying; Lin Changhui etc.; battery, 2006,36 (2): 158-161); and the ratio of the amount of substance of lithium ion, boron and oxalate only is 1.06:1.00:1.95 in the method 1 gained LiBOB product, three kinds of ionic quality percentage compositions and only be 94.68% (seeing DE 19829030).In addition, do not have the participation of water in the method 2 in the entire synthesis process, and not only be solvent in the method shown in the method 1, and reaction process itself also can generate water, thereby make the moisture content of method 1 products obtained therefrom obviously want high than method 2 with water.Therefore, at present a lot of people think that method 2 products obtained therefroms are suitable for the requirement of lithium ion battery electrolyte lithium salts, and method 1 products obtained therefrom is too low and water content is too high can't be applied to lithium ion battery because of main content.Be easy to get than the method divalent is honest and clean but method 1 is raw materials used, and synthetic route simple possible more, so prepare the LiBOB product that lithium ion battery is suitable for, will be of great immediate significance by method of purification 1 products obtained therefrom.
Summary of the invention
The method of purification that the purpose of this invention is to provide a kind of biethyl diacid lithium borate makes biethyl diacid lithium borate reach requirement as the lithium ion battery electrolyte lithium salts.
A kind of method of purification of biethyl diacid lithium borate comprises following processing step:
LiBOB 1. that main content is low, that water content is high is dissolved in drying, heavily steam in the polar aprotic solvent of handling, treat the saturated after-filtration of solution, remove insolubles, filtrate is carried out evaporation concentration, steaming quantity of solvent is 1/20～1/5 of add-on, but the solvent that evaporates through super-dry, heavily after the pre-treatment such as steaming repeated application in this purification process.
2. the solution after will concentrating is freezing 1～5h under-10～-40 ℃ temperature, refrigerating process should slowly be lowered the temperature: constantly the adularescent particulate matter is separated out in temperature-fall period, and the solid matter of separating out separated, isolating method can adopt methods such as filtration, suction filtration, centrifugation, the gained liquid phase can be through distillation, drying after the solid-liquid separation, but heavily after the pre-treatment such as steamings grade repeated application in this purification process.
3. isolating solid matter is placed vacuum drying oven dry, obtain the white particulate solid matter, be the LiBOB product after the purification.
Vacuum drying oven vacuum tightness is 0.06～0.095Mpa, and drying temperature should slowly be increased to the boiling point (temperature should not be higher than the solvent for use boiling point, otherwise the products obtained therefrom caking phenomenon is with especially severe) of selected solvent from room temperature, and be 12～36h time of drying.
Gained LiBOB product can repeatedly be purified with above-mentioned steps again.
The LiBOB raw material that above-mentioned main content is low, water content is high is method 1 a gained LiBOB product noted earlier.
Described polar aprotic solvent is acetonitrile or acetone or tetrahydrofuran (THF).
Method of purification products obtained therefrom of the present invention reaches through infrared spectra
13C with
11The NMR (Nuclear Magnetic Resonance) spectrum of B confirms to be the LiBOB product.
With method 1 gained LiBOB product noted earlier with it be raw material through twice purification after the chemical constitution of LiBOB product measure contrast.Lithium content is with potentiometric titration or flame atomic absorption spectrometry, and the N.F,USP MANNITOL method of boron content after with the calcination product carried out titration determination, and (calcination temperature is 350～500 ℃, and the time is 1～8h), and oxalate content is measured with dichromate titration.The result shows, with 1 prepared LiBOB product as stated above, lithium before purifying, boron, three kinds of mass of ion percentage compositions of oxalate and only be 93.21% (press DE 19829030 and report numerical value, also only be 94.68%), after twice purification, three kinds of mass of ion percentage compositions and greater than 99.30%.
Moisture content with interfere based on the nothing of N-methylformamide the karl Fischer Coulometric Titration (see w.Larsson, J.C.Panitz, A.Cedergren.Talanta, 2006,69:276-280), the metallic impurity ion content is measured by ICP.The result shows that raw material moisture quality percentage composition is 0.10%, and sodium, potassium, calcium, magnesium, weight of iron percentage composition are respectively 0.0034%, 0.0015%, 0.0021%, 0.00060%, 0.0010%; After twice purification, products obtained therefrom moisture quality percentage composition obviously reduces, only be 0.0014%, sodium, potassium, calcium, magnesium, weight of iron percentage composition also decrease, and are lower than 0.0020%, 0.0010%, 0.0010%, 0.00040%, 0.00080% respectively.
From top experimental data as can be seen: the purity of method of purification gained LiBOB product of the present invention has significant improvement, and moisture content and other metallic impurity ion contents also all obviously descend.Therefore, the present invention has realized the purification with method 1 obtained LiBOB product, has solved method 1 gained LiBOB product and can not greatly reduce the LiBOB production cost of products as the difficult problem of lithium ion battery electrolyte lithium salts.Simultaneously, purifying technique of the present invention is simple, operation easily, and reusable after the solvent recuperation, be suitable for industrial mass manufacture.
Embodiment
Embodiment 1, and the 8.10g raw material is added in the pretreated fresh anhydrous acetonitrile of 100mL, is stirred to reach dissolution equilibrium.Filter, remove insolubles.Filtrate is through evaporation concentration (steaming 1/10 of adding quantity of solvent is advisable).Concentrated solution is placed 2h under-10～-35 ℃ of freezing conditions.Carry out solid-liquid separation with the suction filtration method.The gained solid places the dry 30h of vacuum drying oven (vacuum tightness is 0.06～0.095Mpa, and drying temperature slowly rises to 82 ℃ from room temperature), obtains the white particulate solid matter, is the LiBOB product after the purification.Productive rate and analytical results see Table 1.
Embodiment 2, as raw material, repeat example 1 described step with example 1 gained LiBOB product.Gained LiBOB product yield and analytical results see Table 1.
Embodiment 3, as raw material, repeat example 1 described step with example 2 gained LiBOB products.Gained LiBOB product yield and analytical results see Table 1.
Embodiment 4, and the 6.80g raw material is added in the pretreated fresh anhydrous propanone of 100mL, are stirred to reach dissolution equilibrium.Filter, remove insolubles.Filtrate is through evaporation concentration (steam add quantity of solvent 1/20).Concentrated solution liquid is placed 3h under-10～-40 ℃ of freezing conditions.Carry out solid-liquid separation with the suction filtration method.The gained solid places the dry 24h of vacuum drying oven (vacuum tightness is 0.06～0.095Mpa, and drying temperature slowly rises to 57 ℃ from room temperature), obtains the white particulate solid matter.Products obtained therefrom purification as stated above again-inferior.Gained LiBOB product yield and analytical results see Table 1.
Embodiment 5, and the 4.20g raw material is added in the pretreated fresh anhydrous tetrahydro furan of 100mL, are stirred to reach dissolution equilibrium.Filter, remove insolubles.Filtrate is through evaporation concentration (steam add quantity of solvent 1/20).Concentrated solution liquid is placed 3h under-10～-40 ℃ of freezing conditions.Carry out solid-liquid separation with the suction filtration method.The gained solid places the dry 24h of vacuum drying oven (vacuum tightness is 0.06～0.095Mpa, and drying temperature slowly rises to 66 ℃ from room temperature), obtains the white particulate solid matter.Products obtained therefrom is purified once more as stated above.Gained LiBOB product yield and analytical results see Table 1.
Table 1 LiBOB product yield and analytical results
Consider the price, toxicity of selected solvent and can find out that in conjunction with case study on implementation case study on implementation 2 is a best practice.At this moment, can guarantee gained LiBOB product purity, save production cost again to greatest extent.
Claims (3)
1, a kind of method of purification of biethyl diacid lithium borate is characterized in that: biethyl diacid lithium borate earlier that main content is low, that water content is high is dissolved in drying, heavily steams in the polar aprotic solvent of handling, and treats the saturated after-filtration of solution, evaporation concentration; Solution after will concentrating then is freezing 1～5h under-10～-40 ℃ temperature, and places vacuum drying oven dry the gained solid matter, promptly gets the biethyl diacid lithium borate product of purifying; Described polar aprotic solvent is acetonitrile or acetone or tetrahydrofuran (THF).
2, the method for purification of biethyl diacid lithium borate according to claim 1 is characterized in that: steaming quantity of solvent during described evaporation concentration is 1/20～1/5 of add-on.
3, the method for purification of biethyl diacid lithium borate according to claim 1, it is characterized in that: described vacuum drying vacuum tightness is 0.06～0.095Mpa, and drying temperature is the boiling point of room temperature to coordinative solvent, and be 12～36h time of drying.
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| CN100503617C true CN100503617C (en) | 2009-06-24 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168546B (en) * | 2007-11-30 | 2010-06-02 | 张家港市华盛化学有限公司 | Method for preparing Lithium bis(oxalate)borate |
| CN102766151A (en) * | 2011-05-05 | 2012-11-07 | 中国科学院福建物质结构研究所 | Method for purifying lithium bis(oxalate)borate |
| CN102321108A (en) * | 2011-07-18 | 2012-01-18 | 中南大学 | Purification 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19829030C1 (en) * | 1998-06-30 | 1999-10-07 | Metallgesellschaft Ag | Lithium bisoxalatoborate used as conducting salt in lithium ion batteries |
| CN1817888A (en) * | 2006-03-06 | 2006-08-16 | 北京科技大学 | Purification of duplex dicarboxyl-base lithium borate |
-
2006
- 2006-12-11 CN CNB2006101053054A patent/CN100503617C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19829030C1 (en) * | 1998-06-30 | 1999-10-07 | Metallgesellschaft Ag | Lithium bisoxalatoborate used as conducting salt in lithium ion batteries |
| CN1817888A (en) * | 2006-03-06 | 2006-08-16 | 北京科技大学 | Purification of duplex dicarboxyl-base lithium borate |
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