CN113549095A - Preparation process of lithium bis (oxalato) borate - Google Patents
Preparation process of lithium bis (oxalato) borate Download PDFInfo
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- CN113549095A CN113549095A CN202110792439.2A CN202110792439A CN113549095A CN 113549095 A CN113549095 A CN 113549095A CN 202110792439 A CN202110792439 A CN 202110792439A CN 113549095 A CN113549095 A CN 113549095A
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- borate
- oxalato
- lithium bis
- propylene glycol
- dimethyl ether
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 82
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 35
- 238000000746 purification Methods 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 13
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004327 boric acid Substances 0.000 claims abstract description 11
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 87
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 29
- 238000002425 crystallisation Methods 0.000 claims description 28
- 230000008025 crystallization Effects 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002826 coolant Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 20
- 239000012535 impurity Substances 0.000 description 9
- -1 lithium hexafluorophosphate Chemical group 0.000 description 7
- 229910013872 LiPF Inorganic materials 0.000 description 4
- 101150058243 Lipf gene Proteins 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The application discloses a preparation process of lithium bis (oxalato) borate, belongs to the technical field of lithium ion battery material manufacturing, and solves the problem that the purity of a lithium bis (oxalato) borate product prepared by the existing preparation process is low. The preparation method comprises the following steps: s1, feeding reaction: according to the reaction formula (1) LiOH + Li2CO3+6H2C2O4·2H2O＋3H3BO3=3LiBC4O8+23H2O+CO2Adding oxalic acid dihydrate and boric acid into deionized water, and then adding lithium carbonate and lithium hydroxide into the solution to prepare a lithium bis (oxalate) borate solution; s2, drying by distillation; s3, a primary purification process; s4, carrying out secondary purification process, and reasonably adjusting process parameters by carrying out the two-time purification process, so as to obtain the high-purity lithium bis (oxalate) borate product on the premise of ensuring the yield to be more than or equal to 95%.
Description
Technical Field
The application relates to the technical field of lithium ion battery material manufacturing, in particular to a preparation process of lithium bis (oxalato) borate.
Background
The electrolyte is a carrier for ion transmission in the battery and is used for transmitting ions between the positive electrode and the negative electrode of the lithium battery, so that the lithium battery obtains high voltage, high specific energy and the like. Currently, the most widely used electrolyte is lithium hexafluorophosphate (LiPF)6). But lithium hexafluorophosphate (LiPF)6) The thermal stability of (A) is low, and hydrolysis is easy to occur; in addition to this, lithium hexafluorophosphate (LiPF)6) The decomposition can produce hydrofluoric acid, which is harmful to human body and environment, and can dissolve positive metal, which has bad influence on the cycle life and safety performance of the battery.
Lithium bis (oxalato) borate (LiBOB) is a lithium ion battery electrolyte widely used in recent years, and has good thermal stability and chemical stability and wide electrochemical windowAnd lithium bis (oxalato) borate (LiBOB) exhibits good compatibility with typical motor materials. Based on the above advantages, lithium bis (oxalato) borate (LiBOB) is the most likely substitute for lithium hexafluorophosphate (LiPF)6) But is commercially applied to lithium salts in lithium ion batteries. At present, two methods for preparing lithium bis (oxalato) borate (LiBOB) are mainly a liquid phase method and a solid phase method, the solid phase method is mainly synthesized by a lithium source compound, a boron compound and an oxalate compound, and the synthesized lithium bis (oxalato) borate contains more impurities, so that the lithium bis (oxalato) borate can be used only by purification after being synthesized.
The existing purification method is mainly a cooling crystallization method, a crude product is dissolved in an organic solvent, after impurities are filtered, the purity of the lithium bis (oxalato) borate is improved in a cooling crystallization mode, but the impurity removal amount in the purification process is low, so that the purity of the lithium bis (oxalato) borate is low, and the actual production and application are not facilitated.
Disclosure of Invention
In order to reduce the content of impurities in a lithium bis (oxalato) borate product and improve the purity of the lithium bis (oxalato) borate product on the premise of ensuring that the yield is not less than 95%, the application provides a preparation process of the lithium bis (oxalato) borate.
The application provides a preparation process of lithium bis (oxalato) borate, which comprises the following steps:
s1, feeding reaction: adding oxalic acid dihydrate and boric acid into deionized water according to the stoichiometric number in the reaction formula (1), and then adding lithium carbonate and lithium hydroxide into the solution to prepare a lithium bis (oxalate) borate solution;
LiOH+Li2CO3+6H2C2O4·2H2O+3H3BO3＝3LiBC4O8+23H2O+CO2(1)
s2, drying by distillation;
s3, the primary purification process is as follows:
s31, concentration: adding propylene glycol dimethyl ether into the solution treated in the step S2, and filtering; heating and concentrating the filtrate;
s32, crystallization: cooling the solution after the concentration treatment of S31, adding dichloromethane, and stirring until lithium bis (oxalato) borate is crystallized and separated out;
s33, centrifugation: carrying out solid-liquid separation on the solution after crystallization to obtain a primary lithium bis (oxalato) borate crude product;
s4, the secondary purification process comprises the following steps:
s41, concentration: adding propylene glycol dimethyl ether into the primary lithium bis (oxalato) borate crude product obtained in the step S33, and filtering; heating and concentrating the filtrate; wherein the weight part ratio of the propylene glycol dimethyl ether in the step S31 to the propylene glycol dimethyl ether in the step S41 is 1 (1.05-1.2);
s42, crystallization: cooling the solution after the concentration treatment of S41, adding dichloromethane, and stirring until lithium bis (oxalato) borate is crystallized and separated out;
s43, centrifugation: and carrying out solid-liquid separation on the solution after crystallization to obtain the lithium bis (oxalato) borate product.
By adopting the technical scheme, the high-purity lithium bis (oxalate) borate product can be prepared on the premise of ensuring the yield to be more than or equal to 95%. S1 is used for preparing lithium bis (oxalato) borate through neutralization reaction, deionized water in S1 provides a reaction environment for dissolving oxalic acid dihydrate, boric acid, lithium carbonate and lithium hydroxide, the oxalic acid dihydrate and the boric acid are dissolved firstly, and then lithium carbonate and lithium hydroxide are dissolved, so that the generation of local high temperature in the reaction can be avoided, and a by-product metaboric acid is generated, wherein the reaction equation is LiOH + Li2CO3+6H2C2O4·2H2O+ 3H3BO3＝3LiBC4O8+23H2O+CO2. S2, removing the deionized water in the lithium bis (oxalato) borate solution in an evaporation mode. S3 is a primary purification process, S4 is a secondary purification process, the two purification processes are divided into three steps of concentration, crystallization and centrifugation, the method controls the weight part ratio of the propylene glycol dimethyl ether in the step S31 to the propylene glycol dimethyl ether in the step S41, the weight part ratio of the propylene glycol dimethyl ether dichloromethane in the step S3 and the weight part ratio of the propylene glycol dimethyl ether dichloromethane in the step S4 through the synergistic effect of the primary purification process and the secondary purification process, and the premise that the yield is more than or equal to 95 percent is ensuredAnd in addition, the impurity content of the lithium bis (oxalate) borate product is effectively reduced, and the high-purity lithium bis (oxalate) borate is prepared.
Preferably, the weight part ratio of the propylene glycol dimethyl ether in the step S31 to the propylene glycol dimethyl ether in the step S41 is 1: 1.05.
By adopting the technical scheme, the proportion of the propylene glycol dimethyl ether in the step S31 and the step S41 is reasonably controlled, and then the dissolving amount of byproducts and impurities is controlled, so that the purity of the lithium bis (oxalato) borate is improved.
Preferably, in step S3, the weight part ratio of propylene glycol dimethyl ether to dichloromethane is 1: (1.02-1.04); in step S4, the ratio of propylene glycol dimethyl ether to methylene chloride in parts by weight is 1: (1.02-1.04).
Preferably, in step S3, the weight part ratio of propylene glycol dimethyl ether to dichloromethane is 1: 1.02; in step S4, the ratio of propylene glycol dimethyl ether to methylene chloride in parts by weight is 1: 1.02.
by adopting the technical scheme, the ratio of the propylene glycol dimethyl ether to the dichloromethane is controlled, so that the amount of the propylene glycol dimethyl ether dissolved in the dichloromethane is increased, and the purity of the lithium bis (oxalato) borate after the primary purification process and the secondary purification process is improved.
Preferably, in step S31, the concentration temperature is 102-110 ℃, and the concentration time is 1.5-2.5 h.
Preferably, in step S41, the concentration temperature is 112-.
By adopting the technical scheme, the concentration temperature and the concentration time of the step S31 and the step S41 are controlled, the evaporation capacity of propylene glycol dimethyl ether is further controlled, the purity of the lithium bis (oxalato) borate is improved, and in addition, the reaction time is controlled by controlling the concentration temperature and the concentration time, and the production efficiency is improved.
Preferably, the stirring speed of the step S32 is 8-16 rpm/min; step S42 stirring speed is 8-16 rpm/min.
By adopting the technical scheme, the stirring speed has great influence on the purity of the product, and the slow stirring speed can cause the crystallization speed to be too fast, wrap impurities and reduce the purity of the product; too fast a stirring rate can result in slow crystallization rates, less discharge per time, time-consuming stirring, and reduced production rates.
Preferably, the cooling medium of steps S32 and S42 is water.
Preferably, the cooling in step S32 is to 20-28 deg.C and the cooling in step S42 is to 30-40 deg.C.
In summary, the present application has the following beneficial effects:
1. by utilizing the preparation process, the impurity content in the lithium bis (oxalate) borate product is reduced through two purification processes, so that the purity of the lithium bis (oxalate) borate product is effectively improved, the purity of the lithium bis (oxalate) borate product prepared by the preparation process is more than or equal to 99.9%, and the yield is more than or equal to 95%.
2. By reasonably controlling the concentration temperature in the two purification processes, the dissolution amount of by-products and impurities is reduced, and thus the purity of the lithium bis (oxalato) borate is improved.
Detailed Description
The present application will be described in further detail with reference to examples.
Source of raw materials
Lithium carbonate: 99.9% pure, purchased from Shanghai Europe gold practice Co., Ltd.
Lithium hydroxide: 99.9% pure, purchased from Shanghai Europe gold practice Co., Ltd.
Boric acid: 99.5% pure, purchased from Zibo Hengchuang chemical Co.
Oxalic acid dihydrate: 99.6% pure, purchased from jinan Chuangtong chemical company, ltd.
Propylene glycol dimethyl ether: 99% pure, purchased from Shandong Laya chemical Co., Ltd.
Dichloromethane: purchased from Shandong Laya chemical Co., Ltd.
Examples
S1, feeding reaction: adding oxalic acid dihydrate and boric acid into deionized water, stirring until the oxalic acid dihydrate and the boric acid are completely dissolved, and then adding lithium carbonate and lithium hydroxide into the solution to prepare a lithium bis (oxalate) borate solution;
s2, drying by distillation: removing the deionized water in the lithium bis (oxalato) borate solution prepared in the step S1;
s3, the primary purification process is as follows:
s31, concentration: adding propylene glycol dimethyl ether into the solution treated in the step S2, and filtering to obtain filtrate containing propylene glycol dimethyl ether; heating and concentrating the filtrate at the temperature of 102-.
S32, crystallization: cooling the solution after the concentration treatment of S31 to 20-28 ℃, introducing dichloromethane, and stirring until lithium bis (oxalato) borate is crystallized and separated out; wherein the cooling medium is water, the stirring speed is 8-16rpm/min, and the weight part ratio of the propylene glycol dimethyl ether to the dichloromethane is 1: (1.02-1.04).
S33, centrifugation: carrying out solid-liquid separation on the solution after crystallization to obtain a primary lithium bis (oxalato) borate crude product;
s4, the secondary purification process comprises the following steps:
s41, concentration: adding propylene glycol dimethyl ether into the primary lithium bis (oxalato) borate crude product obtained in the step S33, and filtering to obtain filtrate containing propylene glycol dimethyl ether; heating and concentrating the filtrate at the temperature of 112-; wherein, the flow rate of the water is controlled by the control unit.
S42, crystallization: cooling the solution after the concentration treatment of S41 to 30-40 ℃, introducing dichloromethane, and stirring until lithium bis (oxalato) borate is crystallized and separated out; wherein the cooling medium is water, the stirring speed is 8-16rpm/min, the weight part ratio of the propylene glycol dimethyl ether in the step S31 to the propylene glycol dimethyl ether in the step S41 is 1 (1.05-1.2), and the weight part ratio of the propylene glycol dimethyl ether to the dichloromethane in the step S4 is 1: (1.02-1.04).
S43, centrifugation: and carrying out solid-liquid separation on the solution after crystallization to obtain the lithium bis (oxalato) borate product.
Example 1
S1, feeding reaction: preparing 65kg of lithium carbonate, 21kg of lithium hydroxide, 163kg of boric acid, 665kg of oxalic acid dihydrate and 1200kg of deionized water; firstly, adding deionized water into a single-cone kettle through a vacuum pump, manually putting oxalic acid dihydrate and boric acid through a feeding port of the single-cone kettle in a stirring state, and stirring until no obvious particles exist in the solution; after the oxalic acid dihydrate and the boric acid are completely dissolved, manually putting lithium carbonate and lithium hydroxide through a feeding port of the single-cone kettle, and continuously stirring for 0.8h until the reaction materials fully react to prepare a lithium bis (oxalate) borate solution;
s2, drying by distillation: introducing steam into a jacket of the single-cone kettle, controlling the kettle temperature to be 110 ℃, and evaporating the water in the single-cone kettle to dryness by using a water ring vacuum pump under negative pressure; after the water in the single-cone kettle is evaporated to dryness, firstly introducing circulating cooling water into a jacket of the single-cone kettle in a stirring state to reduce the temperature of the kettle to 40 ℃;
s3, primary purification process
S31, concentration: adding 1001kg of propylene glycol dimethyl ether solvent into a single-cone kettle by using a vacuum pump, and after materials in the single-cone kettle are completely dissolved, conveying the solution to a single-cone kettle filter by using a single-cone kettle centrifugal pump for filtering to obtain filtrate containing the propylene glycol dimethyl ether. And (3) conveying the filtrate to a BOB primary crystallization kettle through a centrifugal pump, introducing steam into a jacket of the BOB primary crystallization kettle, controlling the kettle temperature to be 110 ℃, and introducing the steam for 2 hours to evaporate propylene glycol dimethyl ether.
S32, crystallization: circulating cooling water is introduced into a jacket of the BOB primary crystallization kettle to reduce the kettle temperature to 25 ℃; 1021kg of dichloromethane is added into a BOB primary crystallization kettle by a vacuum pump, and the mixture is stirred until lithium bis (oxalato) borate is crystallized and separated out, wherein the stirring speed is 12 rpm/min;
s33, centrifugation: and (4) automatically flowing the crystallized solution to a BOB primary centrifuge for solid-liquid separation to obtain a primary lithium bis (oxalato) borate crude product.
S4 and secondary purification process
S41, concentration: and (3) adding 1051kg of propylene glycol dimethyl ether solvent into the single-cone kettle by using a vacuum pump, and after materials in the single-cone kettle are completely dissolved, conveying the solution to a single-cone kettle filter by using a single-cone kettle centrifugal pump for filtering to obtain filtrate containing the propylene glycol dimethyl ether. And (3) conveying the filtrate to a BOB primary crystallization kettle through a centrifugal pump, introducing steam into a jacket of the BOB primary crystallization kettle, controlling the kettle temperature to be 112 ℃, and introducing the steam for 2 hours to evaporate propylene glycol dimethyl ether.
S42, crystallization: circulating cooling water is introduced into a jacket of the BOB primary crystallization kettle to reduce the kettle temperature to 35 ℃; 10721kg of dichloromethane was pumped by a vacuum pump; adding the solution into a BOB primary crystallization kettle, and stirring until lithium bis (oxalato) borate is crystallized and separated out, wherein the stirring speed is 12 rpm/min;
s43, centrifugation: and (4) automatically flowing the crystallized solution to a BOB primary centrifuge for solid-liquid separation, and separating to obtain the lithium bis (oxalate) borate product.
Examples 2 to 11
The differences between examples 2 to 11 are shown in tables 1 and 2, and the rest is the same as in example 1.
TABLE 1 parameters of examples 1-6
TABLE 2 parameters of example 1 and examples 7-11
Example 12
Example 12 differs from example 1 in that: in step S31, the stirring speed is 8 rpm/min; the stirring rate in step S41 was 8 rpm/min.
Example 13
Example 13 differs from example 1 in that: in step S31, the stirring speed is 16 rpm/min; the stirring rate in step S41 was 16 rpm/min.
Comparative example
Comparative example 1
Comparative example 1 differs from example 1 in that: comparative example 1 did not have the secondary purification process of S4, and after step S33, a lithium bis (oxalato) borate product was obtained.
Comparative example 2
Comparative example 2 differs from example 1 in that: in step S41, the amount of propylene glycol dimethyl ether was 1001 kg.
Comparative example 3
Comparative example 3 differs from example 1 in that: the amount of propylene glycol dimethyl ether in step S41 was 1301 kg.
Comparative example 4
Comparative example 4 differs from example 1 in that: 1001kg of dichloromethane was used in step S3, and 1051kg of dichloromethane was used in S4.
Comparative example 5
Comparative example 5 differs from example 1 in that: the amount of methylene chloride in step S3 was 1101kg, and the amount of methylene chloride in S4 was 1156 kg.
Performance detection
Calculation formula of purity:
and calculating the purity of the lithium bis (oxalato) borate product by using ion chromatography detection.
TABLE 3 purity values for examples 1-13 and comparative examples 1-5
Compared with the comparative example 1, on the premise that the yield is greater than or equal to 95%, the purity of the lithium bis (oxalato) borate prepared in the example 1 is higher than that of the lithium bis (oxalato) borate prepared in the comparative example 1, so that it can be presumed that the purity of the lithium bis (oxalato) borate is improved by two purification processes.
In comparison with comparative examples 2 to 3, the purity of lithium bis (oxalato) borate prepared in example 1 was higher than that of lithium bis (oxalato) borate prepared in comparative examples 2 to 3 under the premise that the yield was 95% or more, and therefore, it can be presumed that the proportional relationship between propylene glycol dimethyl ether in step S31 and propylene glycol dimethyl ether in step S41 affected the purity of lithium bis (oxalato) borate.
Compared with comparative examples 4-5, on the premise that the yield is greater than or equal to 95%, the purity of the lithium bis (oxalato) borate prepared in example 1 is greater than that of the lithium bis (oxalato) borate prepared in comparative examples 4-5, so that it can be presumed that the proportional relationship between the amount of propylene glycol dimethyl ether and the amount of dichloromethane in the primary purification process affects the purity of the lithium bis (oxalato) borate, and the proportional relationship between the amount of propylene glycol dimethyl ether and the amount of dichloromethane in the secondary purification process affects the purity of the lithium bis (oxalato) borate.
Example 1 compared with examples 2 to 3, on the premise that the yield is not less than 95%, the purity of lithium bis (oxalato) borate prepared in example 1 is higher than that of lithium bis (oxalato) borate prepared in comparative examples 2 to 3, and therefore, it can be presumed that the proportional relationship between the amount of propylene glycol dimethyl ether used in the primary purification process and the amount of propylene glycol dimethyl ether used in the secondary purification process affects the purity of lithium bis (oxalato) borate.
Compared with the examples 4 to 5, on the premise that the yield is more than or equal to 95%, the purity of the lithium bis (oxalato) borate prepared in the example 1 is higher than that of the lithium bis (oxalato) borate prepared in the examples 4 to 5, so that the proportional relationship between the amount of propylene glycol dimethyl ether and the amount of dichloromethane in one purification process influences the purity of the lithium bis (oxalato) borate.
Example 1 compared with examples 6 to 7, on the premise that the yield is not less than 95%, the purity of lithium bis (oxalato) borate prepared in example 1 is higher than that of lithium bis (oxalato) borate prepared in examples 6 to 7, and therefore, it can be presumed that the proportional relationship between the amount of propylene glycol dimethyl ether and the amount of dichloromethane in the secondary purification process affects the purity of lithium bis (oxalato) borate.
Example 1 compared with examples 8 to 9, on the premise that the yield was not less than 95%, the purity of lithium bis (oxalato) borate prepared in example 1 was greater than that of lithium bis (oxalato) borate prepared in examples 8 to 9, and therefore it can be presumed that the ratio of the concentration temperature in the primary purification process to the concentration temperature in the secondary purification process affected the purity of lithium bis (oxalato) borate.
Example 1 compared with examples 10 to 11, on the premise that the yield was not less than 95%, the purity of lithium bis (oxalato) borate prepared in example 1 was higher than that of lithium bis (oxalato) borate prepared in examples 10 to 11, and therefore it can be presumed that the concentration temperature in the primary purification process and the concentration temperature in the secondary purification process both affect the purity of lithium bis (oxalato) borate.
In example 1, compared with examples 12 to 13, on the premise that the yield is not less than 95%, the purity of lithium bis (oxalato) borate prepared in example 1 is higher than that of lithium bis (oxalato) borate prepared in examples 12 to 13, and therefore, it can be presumed that the crystallization stirring rate affects the purity of lithium bis (oxalato) borate.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. A preparation process of lithium bis (oxalato) borate is characterized by comprising the following steps:
s1, feeding reaction: adding oxalic acid dihydrate and boric acid into deionized water according to the stoichiometric number in the reaction formula (1), and then adding lithium carbonate and lithium hydroxide into the solution to prepare a lithium bis (oxalate) borate solution;
LiOH＋Li2CO3+6H2C2O4•2H2O＋3H3BO3=3LiBC4O8+23H2O+CO2(1)；
s2, drying by distillation;
s3, the primary purification process is as follows:
s31, concentration: adding propylene glycol dimethyl ether into the solution treated in the step S2, and filtering; heating and concentrating the filtrate;
s32, crystallization: cooling the solution after the concentration treatment of S31, adding dichloromethane, and stirring until lithium bis (oxalato) borate is crystallized and separated out;
s33, centrifugation: carrying out solid-liquid separation on the solution after crystallization to obtain a primary lithium bis (oxalato) borate crude product;
s4, the secondary purification process comprises the following steps:
s41, concentration: adding propylene glycol dimethyl ether into the primary lithium bis (oxalato) borate crude product obtained in the step S33, and filtering; heating and concentrating the filtrate; wherein the weight part ratio of the propylene glycol dimethyl ether in the step S31 to the propylene glycol dimethyl ether in the step S41 is 1 (1.05-1.2);
s42, crystallization: cooling the solution after the concentration treatment of S41, adding dichloromethane, and stirring until lithium bis (oxalato) borate is crystallized and separated out;
s43, centrifugation: and carrying out solid-liquid separation on the solution after crystallization to obtain the lithium bis (oxalato) borate product.
2. The preparation method of lithium bis (oxalato) borate as claimed in claim 1, wherein the weight ratio of propylene glycol dimethyl ether in step S31 to propylene glycol dimethyl ether in step S41 is 1: 1.05.
3. The preparation method of lithium bis (oxalato) borate according to claim 1, wherein in step S3, the ratio of propylene glycol dimethyl ether to dichloromethane in parts by weight is 1: (1.02-1.04);
in step S4, the ratio of propylene glycol dimethyl ether to methylene chloride in parts by weight is 1: (1.02-1.04).
4. The preparation method of lithium bis (oxalato) borate according to claim 3, wherein in step S3, the weight ratio of propylene glycol dimethyl ether to dichloromethane is 1: 1.02;
in step S4, the ratio of propylene glycol dimethyl ether to methylene chloride in parts by weight is 1: 1.02.
5. the method as claimed in claim 1, wherein in step S31, the concentration temperature is 102-110 ℃ and the concentration time is 1.5-2.5 h.
6. The method as claimed in claim 1, wherein in step S41, the concentration temperature is 112-115 ℃ and the concentration time is 2-2.5 h.
7. The preparation method of lithium bis (oxalato) borate according to claim 1, wherein the stirring speed of step S32 is 8-16 rpm/min; step S42 stirring speed is 8-16 rpm/min.
8. The method for preparing lithium bis (oxalato) borate according to claim 1, wherein the cooling medium in step S32 and step S42 is water.
9. The method for preparing lithium bis (oxalato) borate as claimed in claim 1, wherein the cooling temperature in step S32 is 20-28 ℃, and the cooling temperature in step S42 is 30-40 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115974904A (en) * | 2023-01-17 | 2023-04-18 | 福建德尔科技股份有限公司 | Preparation method of lithium bis (oxalato) borate |
| CN116212803A (en) * | 2023-05-10 | 2023-06-06 | 福建德尔科技股份有限公司 | Lithium bisoxalato borate preparation system and control method thereof |
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