CN105541890B - A kind of synthetic method of difluoro oxalate Boratex - Google Patents
A kind of synthetic method of difluoro oxalate Boratex Download PDFInfo
- Publication number
- CN105541890B CN105541890B CN201610054369.XA CN201610054369A CN105541890B CN 105541890 B CN105541890 B CN 105541890B CN 201610054369 A CN201610054369 A CN 201610054369A CN 105541890 B CN105541890 B CN 105541890B
- Authority
- CN
- China
- Prior art keywords
- difluoro oxalate
- boratex
- boric acid
- crude product
- difluoro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- BYKSDPYYTJQZOA-UHFFFAOYSA-N difluoro oxalate Chemical compound FOC(=O)C(=O)OF BYKSDPYYTJQZOA-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000010189 synthetic method Methods 0.000 title claims abstract description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 34
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 15
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 11
- 239000004327 boric acid Substances 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 9
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 9
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 239000012043 crude product Substances 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 229960002645 boric acid Drugs 0.000 description 6
- 235000010338 boric acid Nutrition 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VHSLGFZDYCMVHY-UHFFFAOYSA-N boric acid;oxalyl difluoride Chemical compound OB(O)O.FC(=O)C(F)=O VHSLGFZDYCMVHY-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- QLYGWGQXXSXIQM-UHFFFAOYSA-N OB(O)O.OC(C(O)=O)=O.N.N.N.N.N Chemical compound OB(O)O.OC(C(O)=O)=O.N.N.N.N.N QLYGWGQXXSXIQM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 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 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- -1 oxalic acid ammonium salt compound Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- VORGUAVDPHGXSU-UHFFFAOYSA-N OB(O)O.O=C(C(OF)=O)OF.N.N.N Chemical compound OB(O)O.O=C(C(OF)=O)OF.N.N.N VORGUAVDPHGXSU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- CZCSLHYZEQSUNV-UHFFFAOYSA-N [Na].OB(O)O Chemical compound [Na].OB(O)O CZCSLHYZEQSUNV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KWWDVIIKMNQADG-UHFFFAOYSA-N boric acid;difluoro oxalate Chemical compound OB(O)O.FOC(=O)C(=O)OF KWWDVIIKMNQADG-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 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)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of synthetic method of difluoro oxalate Boratex, belong to electrochemical field.The synthetic method adds sodium fluoride, oxalic acid and hydrogen fluoride in the aqueous solution of boric acid, form homogeneous mixed aqueous solution, it is evaporated and obtains white precipitate, then carry out thoroughly being dried to obtain crude product, obtained crude product is extracted in acetonitrile or ether solvent, extract evaporative crystallization is finally obtained into final products difluoro oxalate Boratex.
Description
Technical field
The present invention relates to a kind of synthetic method of difluoro oxalate Boratex, belong to electrochemical field.
Background technology
The lithium rechargeable battery of development comparative maturity has energy density high at present, has extended cycle life, self discharge is small etc.
Advantage, is widely used as the working power of various portable electronic products（Mobile phone, palm PC etc.）, and gradually application is portable dress
Standby electrokinetic cell（Electric car, submarine etc.）.But, global lithium resource is not rich, and abundance is only 0.006% in the earth's crust, together
When skewness, the suffering as following large-scale application.
Compared with lithium resource, sodium reserves very abundant, crustal abundance is about 2.64%, also there is substantial amounts of sodium in seawater.Simultaneously
Sodium and lithium are same major element, and chemical property is close, and the recycling of sodium is more ripe cheap, substitutes lithium with sodium, opens
Hair sodium ion secondary battery has broad application prospects.For sodium-ion battery, it is to close very much to develop high performance electrolyte
The link of key, and high performance sodium salt is the important component for constituting electrolyte.It is applied to sodium ion electrolyte material at present
Sodium salt in material mainly has sodium hexafluoro phosphate and sodium perchlorate, and the two is bad for the resistance of micro-moisture, therefore electrolysis material
Although expecting that ionic conductivity is higher, less stable so that the final cycle performance of battery is bad, does not reach use requirement.
In lithium-ion electrolyte material, boron system lithium salts such as di-oxalate lithium borate and difluorine oxalic acid boracic acid lithium has preferable for moisture
Resistance, excellent combination property.Preparing corresponding sodium salt just has very high practical value.But, on the other hand, directly utilize lithium
When the preparation method of salt removes to prepare sodium salt, conversion ratio is very low, and this is accomplished by developing proprietary preparation technology for specific sodium salt.
DocumentJournal of Power Sources 237: 104-111.Disclose a kind of based on organic reactant
The synthetic method of second mate's oxalic acid Boratex, concrete technology will be filtered simultaneously after sodium oxalate and boron trifluoride reaction in diethyl ether solution
Solvent is drained, it has the disadvantage the organic reactant and lower boiling organic solvent that employ costliness, the security of operation is difficult to protect
Card, while longer reflux time causes experimentation higher.
Chinese patentCN103483367AA kind of method for preparing difluoro oxalic acid boric acid metal salt is disclosed, is specifically to contain
Boron compound and oxalic acid ammonium salt compound carry out reaction synthesis dihalo oxalic acid boric acid ammonium salt or dialkoxy oxalic acid boric acid ammonium salt,
Then prepare difluoro oxalate boric acid ammonium salt with fluorination reagent reaction, products therefrom and appropriate MxCO3 or M (OH) y (M=Li, Na,
When K, Rb, Cs, x=2, y=1；When M=Mg, Zn, x=1, y=2) reacted obtains difluoro oxalic acid boric acid metal salt, by tying again
The difluoro oxalic acid boric acid metal salt product of high-purity is obtained after crystalline substance purification.
The content of the invention
The present invention is intended to provide a kind of synthetic method of difluoro oxalate Boratex, discloses a kind of mix in aqueous in fact
Existing reactant homogeneous reaction, the extraction of active component is realized with reference to organic solvent, the method for finally giving high quality of products.Solve
Cost and conversion ratio problem present in prior art,
The invention provides a kind of synthetic method of difluoro oxalate Boratex, fluorination is added first in the aqueous solution of boric acid
Sodium, oxalic acid and hydrogen fluoride, form homogeneous mixed aqueous solution, are evaporated and obtain white precipitate, then carry out thoroughly being dried to obtain slightly
Product, obtained crude product is extracted in acetonitrile or ether solvent, is finally finally produced extract evaporative crystallization
Product difluoro oxalate Boratex.The mol ratio of the raw material is：Boric acid：Sodium fluoride：Oxalic acid：Hydrogen fluoride=1:1:1:1.
The synthetic method that the present invention is provided, processing step is：
（1）According to the stoichiometric proportion of each element in difluoro oxalate Boratex, boric acid is added in deionized water first, and
70 DEG C ~ 90 DEG C are heated to, the concentration of boric acid is 0.5mol/L, and sodium fluoride, hydrogen fluoride and oxalic acid are added afterwards, 1-4h is stirred；
（2）Moisture is evaporated after stirring, it is 50 ~ 95 DEG C to control temperature, the time is 12h ~ 36h, relative degree of vacuum is -80kPa
~ -95kPa, obtains crude product；
（3）Obtained crude product is transferred in ether or acetonitrile, 30 DEG C ~ 80 DEG C are heated to, and stirs 1 ~ 4h, will be organic
The filtrate that solution is filtrated to get is evaporated crystallization and obtains the difluoro oxalate Boratex that purity reaches 99%.
W-response can be used to lower chemical equation to describe：
NaF+HF+H3BO3+H2C2O4→NaBF2C2O4+3H2O
The present invention is using mixing, and accessory substance is seldom so that conversion ratio is significantly improved compared with other techniques.While this method
Time-consuming reflux operation is not used, the overall used time significantly shortens.
Brief description of the drawings
Fig. 1 is the infrared spectrogram for the difluoro oxalate Boratex that embodiment 1 is prepared.
Fig. 2 is the thermogravimetric curve figure for the difluoro oxalate Boratex that embodiment 1 is prepared.
Fig. 3 is the XRD spectra for the difluoro oxalate Boratex that embodiment 2 is prepared.
Fig. 4 is that the difluoro oxalate Boratex that embodiment 2 is prepared is dissolved in mixed solvent EC/PC=1:1 liquid prepared
The electrical conductivity temperature curve of state electrolyte.
Fig. 5 is that the difluoro oxalate Boratex that embodiment 2 is prepared is dissolved in mixed solvent EC/PC=1:1 liquid prepared
State electrolyte is applied to the cycle performance curve of experimental cell.
Embodiment
The present invention is further illustrated below by embodiment, but is not limited to following examples.
Embodiment 1：
（1）It is tetrafluoro container to select reactor, adds 123.66g boric acid in 4L deionized waters, and is heated to 80 DEG C, starts to stir
Mix.
（2）The oxalic acid 252.12g containing two crystallizations water is added, it is 36% that stirring adds mass concentration until completely dissolved
Hydrofluoric acid 111.2g, and sodium fluoride 83.98g, stirring reaction 4h.
（3）The aqueous solution is transferred in Rotary Evaporators, temperature is set to 85 DEG C, and vacuum is -90kPa, is evaporated 24h, obtains
To white solid.
（4）Obtained white solid is transferred in 2L ether, filtered after being heated to 30 degree, stirring 2h.
（5）For obtained filtrate under the conditions of 30 degree evaporation solvent, obtain difluoro oxalate Boratex about 265g, once turn
Rate about 82.8%, purity about 99%.
The infrared spectrogram of the difluoro oxalate Boratex prepared by the present embodiment as shown in Figure 1, provides difluoro in figure
The infrared spectrogram of Lithium bis (oxalate) borate is for reference.
Fig. 2 is the thermogravimetric curve figure for the difluoro oxalate Boratex that embodiment 1 is prepared, and illustrates difluoro oxalate Boratex
Just start significantly decomposition more than 250 degree, with preferable heat endurance.
Embodiment 2：
（1）It is tetrafluoro container to select reactor, adds 92.75g boric acid in 2L deionized waters, and is heated to 90 DEG C, starts to stir
Mix.
（2）The hydrofluoric acid 83.4g that mass concentration is 36% is added, the oxalic acid 189.09g containing two crystallizations water is added, stirs
Mix until completely dissolved, and sodium fluoride 62.98g, stirring reaction 2h.
（3）The aqueous solution is transferred in Rotary Evaporators, temperature is set to 80 degrees Celsius, and vacuum is -95kPa, is evaporated
36h, obtains white solid.
（4）Obtained white solid is transferred in 2L acetonitriles, filtered after being heated to 70 degree, stirring 4h.
（5）For obtained filtrate under the conditions of 50 degree evaporation solvent, obtain difluoro oxalate Boratex about 218g, once turn
Rate about 91.6%, purity about 98%.
Fig. 3 shows the XRD spectra for the difluoro oxalate Boratex that the present embodiment is prepared, and diffraction maximum is sharply obtained
Preferable difluoro oxalate boric acid sodium crystal, and occur without obvious dephasign peak.
Fig. 4 is that the difluoro oxalate Boratex that the present embodiment is prepared is dissolved in mixed solvent EC/PC=1:1 liquid prepared
The electrical conductivity temperature curve of state electrolyte, it can be seen that its conductivity at room temperature reaches 10-3More than S/cm, meets secondary cell
For the requirement of electrolytic conductivity.
Fig. 5 is that the difluoro oxalate Boratex that the present embodiment is prepared is dissolved in mixed solvent EC/PC=1:1 liquid prepared
State electrolyte is applied to the cycle performance curve of experimental cell, it is seen that use difluoro oxalate Boratex for the electrolyte of electrolyte salt
With excellent cycle performance of battery.The difluoro oxalate boric acid proposed as a kind of electrolyte of excellent performance, patent of the present invention
Electrolyte prepared by sodium salt can be used in sodium ion secondary battery and super capacitor.
Claims (1)
1. a kind of synthetic method of difluoro oxalate Boratex, it is characterised in that：First in the aqueous solution of boric acid add sodium fluoride,
Oxalic acid and hydrogen fluoride, form homogeneous mixed aqueous solution, are evaporated and obtain white precipitate, be then thoroughly dried to obtain thick production
Product, obtained crude product is extracted in acetonitrile or ether solvent, and extract evaporative crystallization finally is obtained into final products
Difluoro oxalate Boratex；The mol ratio of the raw material is：Boric acid：Sodium fluoride：Oxalic acid：Hydrogen fluoride=1:1:1:1；Specifically include with
Lower step：
（1）According to the stoichiometric proportion of each element in difluoro oxalate Boratex, boric acid is added in deionized water first, and heat
To 70 DEG C ~ 90 DEG C, the concentration of boric acid is 0.5mol/L, then adds sodium fluoride, hydrogen fluoride and oxalic acid, stirs 1-4h；
（2）Moisture is evaporated after stirring, control temperature be 50 ~ 95 DEG C, the time be 12h ~ 36h, relative degree of vacuum be -80kPa ~ -
95kPa, obtains crude product；
（3）Obtained crude product is transferred in ether or acetonitrile, 30 DEG C ~ 80 DEG C are heated to, and stirs 1 ~ 4h, by organic solution
The filtrate being filtrated to get is evaporated crystallization and obtains the difluoro oxalate Boratex that purity reaches 99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610054369.XA CN105541890B (en) | 2016-01-27 | 2016-01-27 | A kind of synthetic method of difluoro oxalate Boratex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610054369.XA CN105541890B (en) | 2016-01-27 | 2016-01-27 | A kind of synthetic method of difluoro oxalate Boratex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105541890A CN105541890A (en) | 2016-05-04 |
| CN105541890B true CN105541890B (en) | 2017-08-29 |
Family
ID=55821495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610054369.XA Active CN105541890B (en) | 2016-01-27 | 2016-01-27 | A kind of synthetic method of difluoro oxalate Boratex |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105541890B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112534618A (en) * | 2018-06-18 | 2021-03-19 | 法国国家科学研究中心 | Novel electrolyte compositions for sodium-ion batteries |
| CN111592559A (en) * | 2020-05-22 | 2020-08-28 | 兰州理工大学 | Method for synthesizing sodium difluorooxalate through one-step method |
| CN117321061A (en) * | 2022-06-24 | 2023-12-29 | 时代思康新材料有限公司 | Sodium difluoro oxalate borate, and preparation method and application thereof |
| CN115304629B (en) * | 2022-10-09 | 2023-06-02 | 江苏国泰超威新材料有限公司 | Preparation method of difluoro oxalic acid sodium borate |
| CN115676855B (en) * | 2022-12-30 | 2023-04-11 | 江苏华盛锂电材料股份有限公司 | Preparation method of sodium ion battery electrolyte sodium salt |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265569A (en) * | 2013-05-17 | 2013-08-28 | 太原理工大学 | Lithium difluoro(oxalato)borate synthesis method |
| CN103342711A (en) * | 2011-06-22 | 2013-10-09 | 蒋盘君 | Preparation method for LiODFB (lithium difluoroborate) electrolyte salt by utilizing simple preparation process |
| CN103483367A (en) * | 2013-09-17 | 2014-01-01 | 上海璞泰来新材料技术有限公司 | Preparing method of difluoro oxalic acid boric acid metal salt |
| CN104185636A (en) * | 2011-11-14 | 2014-12-03 | 罗克伍德锂有限责任公司 | Process for preparing metal difluorochelatoborates and use as battery electrolytes or additives in electrochemical cells |
-
2016
- 2016-01-27 CN CN201610054369.XA patent/CN105541890B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103342711A (en) * | 2011-06-22 | 2013-10-09 | 蒋盘君 | Preparation method for LiODFB (lithium difluoroborate) electrolyte salt by utilizing simple preparation process |
| CN104185636A (en) * | 2011-11-14 | 2014-12-03 | 罗克伍德锂有限责任公司 | Process for preparing metal difluorochelatoborates and use as battery electrolytes or additives in electrochemical cells |
| CN103265569A (en) * | 2013-05-17 | 2013-08-28 | 太原理工大学 | Lithium difluoro(oxalato)borate synthesis method |
| CN103483367A (en) * | 2013-09-17 | 2014-01-01 | 上海璞泰来新材料技术有限公司 | Preparing method of difluoro oxalic acid boric acid metal salt |
Non-Patent Citations (2)
| Title |
|---|
| "N-Alkyl-N- methylpyrrolidinium difluoro(oxalato)borate ionic liquids: physical/electrochemical properties and Al corrosion";Allen J L. et al;《Journal of Power Sources》;20130314;第237卷;第105页右栏第2段 * |
| "Sodium-difluoro(oxalato)borate (NaDFOB): a new electrolyte salt for Na-ion batteries";Chen J E. et al;《Chem. Commun》;20150507;第51卷;第9809-9812页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105541890A (en) | 2016-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105541890B (en) | A kind of synthetic method of difluoro oxalate Boratex | |
| Ji | A perspective of ZnCl2 electrolytes: the physical and electrochemical properties | |
| Battistel et al. | Electrochemical methods for lithium recovery: a comprehensive and critical review | |
| CN100593515C (en) | Method of preparing waterless lithium terafluoroborate | |
| Zhao et al. | Li extraction from high Mg/Li ratio brine with LiFePO4/FePO4 as electrode materials | |
| CN107201452B (en) | One kind being based on LiMn2O4The method that electrode material mentions lithium from lithium-containing solution | |
| Mandai et al. | A key concept of utilization of both non-Grignard magnesium chloride and imide salts for rechargeable Mg battery electrolytes | |
| CN102803142B (en) | The manufacture method of tetrafluoroborate | |
| CN102826563A (en) | Preparation method of high-purity lithium tetrafluoroborate | |
| CN104282908A (en) | Method for synthesizing high-sodium iron-based Prussian blue electrode material | |
| JP3875053B2 (en) | ELECTRODE MATERIAL, ITS MANUFACTURING METHOD, AND BATTERY USING THE SAME | |
| CN103030657A (en) | Preparation method of electrolyte double-oxalate based lithium borate for lithium ion battery | |
| CN105449177B (en) | A kind of porous cube of ZnSnO for sodium-ion battery3@graphene negative materials and preparation method thereof | |
| CN102993119A (en) | Imidazole-containing ionic liquid and preparation method thereof, and electrolyte and application thereof | |
| Kijima et al. | Lithium ion insertion and extraction reactions with Hollandite-type manganese dioxide free from any stabilizing cations in its tunnel cavity | |
| US9077037B2 (en) | Electrode and electrolyte materials for batteries | |
| CN104557995B (en) | Preparation method of lithium oxalyldifluoroborate | |
| CN103227326B (en) | Synthesis method of lithium hexafluorozirconate and new application thereof | |
| Fu et al. | V2O5 as a versatile electrode material for postlithium energy storage systems | |
| CN102694162A (en) | Lithium iron titanate cathode material for lithium-ion secondary battery and hydrothermal synthesis preparation method thereof | |
| CN110305153A (en) | A kind of synthetic method and application of double oxalic acid Boratexes | |
| Bankole et al. | Silicon exchange effects of glassware on the recovery of LiPF6: Alternative route to preparation of Li2SiF6 | |
| CN102993118B (en) | Piperidine-containing ionic liquid and preparation method thereof, and electrolyte and application thereof | |
| Niu et al. | Structure Evolution of V2O5 as Electrode Materials for Metal‐Ion Batteries | |
| CN103265569A (en) | Lithium difluoro(oxalato)borate synthesis method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |