CN109659608A - A kind of preparation method and application of tetrafluoro lithium aluminate - Google Patents
A kind of preparation method and application of tetrafluoro lithium aluminate Download PDFInfo
- Publication number
- CN109659608A CN109659608A CN201811367089.XA CN201811367089A CN109659608A CN 109659608 A CN109659608 A CN 109659608A CN 201811367089 A CN201811367089 A CN 201811367089A CN 109659608 A CN109659608 A CN 109659608A
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- Prior art keywords
- lithium aluminate
- preparation
- tetrafluoro
- tetrafluoro lithium
- lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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 present invention relates to a kind of preparation method and applications of tetrafluoro lithium aluminate to be added Al (NO in molar ratio in vacuum calcining furnace at 1: 4: 13)3、NH4F、LiNO3Powder, calcination temperature are 300 DEG C~600 DEG C, and calcination time is 4~8 hours, after cooling under inert gas protection, are dissolved, are filtered using organic solvent, recrystallized, being dried to obtain tetrafluoro lithium aluminate product.Use lithium-ion battery electrolytes of the invention, manufactured lithium ion battery has high operating voltage (5V~5.5V), improve the energy density of lithium ion battery, tetrafluoro lithium aluminate is capable of forming the CEI film for stablizing densification in positive electrode surface simultaneously, so as to greatly improve the cycle life of battery under high voltages.Tetrafluoro lithium aluminate preparation method of the invention is simple, and material source is extensive, and the processing is simple in lithium-ion battery electrolytes for products obtained therefrom, has excellent performance, and is suitable for lithium-ion battery electrolytes and is mass produced.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of additive four of lithium-ion battery electrolytes
The preparation method and application of fluoaluminic acid lithium.
Background technique
Into the second half in 20th century, global Main Auto market after undergoing oil crisis three times in succession, new-energy automobile
Into the visual field of vehicle enterprise and the public.New-energy automobile uses lithium ion battery as active force source at this stage, and electric car exists
Continually develop that mass is lighter, volume is smaller, output voltage and the higher lithium ion battery of power density, so developing high-energy
The lithium ion battery of density is the important R&D direction of lithium battery industry.The lithium ion battery for designing high-energy density, is removed
Its space utilization rate is continued to optimize, the compacted density and gram volume of battery plus-negative plate material is improved, uses High-conductivity carbon
Nanometer and polymeric adhesive come improve anode and negative electrode active material content outside, can also be promoted lithium ion battery work when
Operating voltage.
Used currently, the lithium ion battery of 4.35V and 4.4V is mature on the market, 4.45V and 4.5V also start by
Market favor, gradually can mature get up.But the battery of 4.5V and the above voltage is limited by positive electrode and electrolyte, at present
It is also difficult to reach.
Summary of the invention
One of goal of the invention of the invention is to provide a kind of preparation method of higher tetrafluoro lithium aluminate of purity；
The two of goal of the invention of the invention are to provide application of the above-mentioned tetrafluoro lithium aluminate in battery electrolyte.
Technical scheme is as follows:
In vacuum calcining furnace, Al (NO is added3)3、NH4F、LiNO3Powder is calcined, cooling, in inertia after cooling
It under gas shield, is dissolved, is filtered using organic solvent, recrystallization is dried to obtain tetrafluoro lithium aluminate.
Preferably, powder proportions Al (NO in molar ratio3)3: NH4F:LiNO31: (4-5): (0.8-1.2) is uniformly mixed.
Preferably, calcination temperature is 300~600 DEG C；
Preferably, calcination time is 4~8 hours；
Preferably, inert gas is one kind of nitrogen or argon gas；
Preferably, organic solvent is one kind of propene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate
Or it is several.Further, organic solvent can be the mixed solution of propene carbonate and dimethyl carbonate.
The present invention also provides a kind of application of tetrafluoro lithium aluminate in battery electrolyte, electrolyte includes following components,
Tetrafluoro lithium aluminate mass ratio is 0.5%~5%；Electrolytic salt mass ratio is 10%~16%；Organic solvent mass ratio is 75%
~88.5%.
Preferably, electrolytic salt is LiPF6、LiPO2F2, one or more of LiDFOB, LiBOB；
Preferably, organic solvent is ethylene carbonate, propene carbonate, diethyl carbonate, sulfolane, the first and second sulfones, two
Two or more mixture of methyl sulfone.
Using battery electrolyte of the invention, there is broader electrochemical window, have extended cycle life.
Tetrafluoro lithium aluminate preparation process flow that the present invention obtained have the beneficial effect that is simple, required equipment be market at
Ripe equipment, production process generation exhaust gas synthesize ammonium class fertilizer after can recycling by device, after organic solvent can be by rectifying
It reuses, no other pollutions.The tetrafluoro lithium aluminate purity is high of preparation, impurity is few, and no other metal ions introduce.Party's legal system
The lithium battery electrolytes of standby tetrafluoro lithium aluminate have broader electrochemical window (2.0V~5.5V), and matching 5.0V high voltage is just
After battery is made in pole, 80% battery normal temperature circulation service life 1C@3.0V~5.0V be can achieve 2000 times.
Detailed description of the invention
Fig. 1 is test cell discharge curve；
Fig. 2 is test cell 1C cyclic curve.
Specific embodiment
Embodiment 1
Prepare tetrafluoro lithium aluminate: by Al (NO3)3、NH4F、LiNO3Powder in molar ratio 1: 4: l, i.e. quality are Al (NO3)3∶
375.13KG,NH4F∶148KG,LiNO3: 68.95KG in rotary type vacuum calcining furnace, opens vacuum, rotation after mixing,
300 DEG C are warming up to, is sintered 4 hours.It cools to 60 DEG C hereinafter, under nitrogen protection, being transferred to stirring with cooling water jecket
It mixes in kettle, the mixed solution of suitable dimethyl carbonate and propene carbonate, dissolution is added according to dissolution situation in a stirring kettle
It is 12 mu-metal filters by aperture after completely, evaporation is entered after filtering, recrystallizes, is filling after drying integrated equipment processing
Into stainless steel barrel to get tetrafluoro lithium aluminate finished product 100KG.
Using the preparation of the electrolyte of tetrafluoro lithium aluminate, quality ethylene carbonate is pressed in glove box under nitrogen protection
Mixed liquor is made in 272g, methyl ethyl carbonate 272g, diethyl carbonate 271g, with liquid nitrogen frozen to 0 DEG C hereinafter, mixed liquor side freezes
While being slowly added to 125g LiPF6, the tetrafluoro lithium aluminate of 20g is then added, other additives: carbonic acid Asia second then are being added
Enester 20g, 1,3- propane sultone 20g, stirring and dissolving is uniform, obtains the lithium ion battery that 1KG contains tetrafluoro lithium aluminate
Electrolyte.
Embodiment 2
Prepare tetrafluoro lithium aluminate: by Al (NO3)3、NH4F、LiNO3Powder is Al (NO by quality3)3∶375.13KG,NH4F∶
185KG,LiNO3: 82.74KG in rotary type vacuum calcining furnace, opens vacuum, rotation, is warming up to 400 DEG C after mixing,
Sintering 6 hours.It cools to 60 DEG C hereinafter, under nitrogen protection, be transferred in the stirred tank with cooling water jecket, is stirring
Suitable methyl ethyl carbonate is added according to dissolution situation in kettle, is 12 mu-metal filters, filtering by aperture after dissolution completely
Afterwards enter evaporation, recrystallization, drying integrated equipment processing after it is filling into stainless steel barrel to get tetrafluoro lithium aluminate finished product
110KG。
Using the preparation of the electrolyte of tetrafluoro lithium aluminate, quality diethyl carbonate is pressed in glove box under nitrogen protection
Mixed liquor is made in 272g, sulfolane 270g, dimethyl sulfone 271g, with liquid nitrogen frozen to 0 DEG C hereinafter, mixed liquor is slow in freezing
125g LiPO is added2F2, the tetrafluoro lithium aluminate of 20g is then added, other additives: vinylene carbonate then are being added
20g, 1,3- propane sultone 20g, stirring and dissolving is uniform, obtains the lithium ion battery electrolysis that 1KG contains tetrafluoro lithium aluminate
Liquid.
With above-mentioned battery electrolyte at stacked soft-package battery, battery nominal capacity is 700mAh.Battery is carried out
Electric performance test.After test result is as shown, be added tetrafluoro lithium aluminate, battery life has extension.
Claims (10)
1. a kind of preparation method of tetrafluoro lithium aluminate, comprises the following steps: Al (NO being added in vacuum calcining furnace3)3、NH4F、
LiNO3Powder is calcined, cooling, after cooling under inert gas protection, uses organic solvent dissolution, filtering, recrystallization, drying
Obtain tetrafluoro lithium aluminate product.
2. a kind of preparation method of tetrafluoro lithium aluminate according to claim 1, it is characterised in that: the Al (NO3)3、NH4F、
LiNO3Powder proportions in molar ratio 1: (4-5): (0.8-1.2) is uniformly mixed.
3. a kind of preparation method of tetrafluoro lithium aluminate according to claim 1, it is characterised in that: the calcination temperature is 300
~600 DEG C.
4. a kind of preparation method of tetrafluoro lithium aluminate according to claim 1, it is characterised in that: the calcination time is 4~8
Hour.
5. a kind of preparation method of tetrafluoro lithium aluminate according to claim 1, it is characterised in that: the inert gas is nitrogen
Or one kind of argon gas.
6. a kind of preparation method of tetrafluoro lithium aluminate according to claim 1, it is characterised in that: the organic solvent is carbonic acid
The one or more of acrylic ester, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate.
7. a kind of preparation method of tetrafluoro lithium aluminate according to claim 6, it is characterised in that: the organic solvent is carbonic acid
The mixed solution of acrylic ester, dimethyl carbonate.
8. application of the tetrafluoro lithium aluminate in battery electrolyte, feature made from preparation method according to claim 1
Be: the electrolyte includes following components, and tetrafluoro lithium aluminate mass ratio is 0.5%~5%；Electrolytic salt mass ratio is 10%
~16%；Organic solvent mass ratio is 75%~88.5%.
9. application of the tetrafluoro lithium aluminate in battery electrolyte, feature made from preparation method according to claim 8
Be: the electrolytic salt is LiPF6、LiPO2F2, one or more of LiDFOB, LiBOB.
10. application of the tetrafluoro lithium aluminate in battery electrolyte, feature made from preparation method according to claim 8
Be: the organic solvent is ethylene carbonate, propene carbonate, diethyl carbonate, sulfolane, the first and second sulfones, dimethyl sulfone
Two or more mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201811367089.XA CN109659608A (en) | 2018-11-16 | 2018-11-16 | A kind of preparation method and application of tetrafluoro lithium aluminate |
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| CN201811367089.XA CN109659608A (en) | 2018-11-16 | 2018-11-16 | A kind of preparation method and application of tetrafluoro lithium aluminate |
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| CN201811367089.XA Pending CN109659608A (en) | 2018-11-16 | 2018-11-16 | A kind of preparation method and application of tetrafluoro lithium aluminate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110395750A (en) * | 2019-08-09 | 2019-11-01 | 湖北锂诺新能源科技有限公司 | The preparation method of trifluoromethyl sulfonic acid lithium as lithium ion battery electrolyte |
Citations (8)
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|---|---|---|---|---|
| FR2067209A1 (en) * | 1969-11-25 | 1971-08-20 | Ugine Kuhlmann | Anhydrous aluminium fluoride prepn |
| GB1463267A (en) * | 1974-10-28 | 1977-02-02 | Central Glass Co Ltd | Process for preparation of ammonium tetrafluoroaluminate |
| US4367267A (en) * | 1980-04-25 | 1983-01-04 | Hitachi, Ltd. | Amorphous lithium fluoaluminate |
| CN103570050A (en) * | 2012-09-19 | 2014-02-12 | 东北林业大学 | Lithium hexafluoride calcium aluminium material with hollow tetrakaidecahedron structure |
| CN103733412A (en) * | 2011-02-04 | 2014-04-16 | 丰田自动车工程及制造北美公司 | High voltage battery for a lithium battery |
| CN104326482A (en) * | 2013-07-23 | 2015-02-04 | 上海中锂实业有限公司 | Lithium tetrafluoroborate preparation method |
| CN106335907A (en) * | 2016-08-27 | 2017-01-18 | 洛阳和梦科技有限公司 | Catalytic synthesis method of lithium tetrafluoroborate |
| CN107585776A (en) * | 2017-10-13 | 2018-01-16 | 湖北省宏源药业科技股份有限公司 | A kind of method of Rheological Phase Method synthesis LiBF4 |
-
2018
- 2018-11-16 CN CN201811367089.XA patent/CN109659608A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2067209A1 (en) * | 1969-11-25 | 1971-08-20 | Ugine Kuhlmann | Anhydrous aluminium fluoride prepn |
| GB1463267A (en) * | 1974-10-28 | 1977-02-02 | Central Glass Co Ltd | Process for preparation of ammonium tetrafluoroaluminate |
| US4367267A (en) * | 1980-04-25 | 1983-01-04 | Hitachi, Ltd. | Amorphous lithium fluoaluminate |
| CN103733412A (en) * | 2011-02-04 | 2014-04-16 | 丰田自动车工程及制造北美公司 | High voltage battery for a lithium battery |
| CN103570050A (en) * | 2012-09-19 | 2014-02-12 | 东北林业大学 | Lithium hexafluoride calcium aluminium material with hollow tetrakaidecahedron structure |
| CN104326482A (en) * | 2013-07-23 | 2015-02-04 | 上海中锂实业有限公司 | Lithium tetrafluoroborate preparation method |
| CN106335907A (en) * | 2016-08-27 | 2017-01-18 | 洛阳和梦科技有限公司 | Catalytic synthesis method of lithium tetrafluoroborate |
| CN107585776A (en) * | 2017-10-13 | 2018-01-16 | 湖北省宏源药业科技股份有限公司 | A kind of method of Rheological Phase Method synthesis LiBF4 |
Non-Patent Citations (1)
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| G GARTON，ET AL.: "Some observations on the tetrafluoroaluminates of lithium and sodium", 《JOURNAL OF INORGANIC AND NUCLEAR CHEMISTRY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110395750A (en) * | 2019-08-09 | 2019-11-01 | 湖北锂诺新能源科技有限公司 | The preparation method of trifluoromethyl sulfonic acid lithium as lithium ion battery electrolyte |
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