CN111048832A - Lithium iron phosphate long-life battery electrolyte for energy storage - Google Patents
Lithium iron phosphate long-life battery electrolyte for energy storage Download PDFInfo
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- CN111048832A CN111048832A CN201911001395.6A CN201911001395A CN111048832A CN 111048832 A CN111048832 A CN 111048832A CN 201911001395 A CN201911001395 A CN 201911001395A CN 111048832 A CN111048832 A CN 111048832A
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- Prior art keywords
- lithium
- iron phosphate
- electrolyte
- carbonate
- lithium iron
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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
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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
- H01M10/052—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
- H01M10/05—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
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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 invention discloses lithium iron phosphate long-life battery electrolyte for energy storage, which mainly comprises lithium salt, an organic solvent and a composite synergistic film-forming additive, wherein the lithium salt of the electrolyte is lithium hexafluorophosphate, lithium difluoroborate, lithium perchlorate, lithium tetrafluoroborate and the like, and the organic solvent comprises cyclic carbonate and chain carbonate. The electrolyte is applied to the lithium ion battery, can prolong the normal-temperature and high-temperature cycle life of the battery, and completely meets the national standard electrical property and safety performance.
Description
Technical Field
The invention relates to the field of electrochemistry, in particular to lithium iron phosphate long-life battery electrolyte for energy storage.
Background
The cycle performance of the lithium ion battery is an important performance index for inspecting the battery. At present, in consideration of the electrolyte, the prior art scheme for improving the cycle performance of the battery is to add a single negative electrode film-forming additive into the electrolyte, so that an SEI (solid electrolyte interphase) protective film is formed on a negative electrode in the battery cycle process, and side reactions between the electrolyte and the negative electrode are reduced.
In the prior art, only one negative film-forming agent is generally added in the conventional commercial lithium iron phosphate battery electrolyte, and in the circulation process, due to the increase of side reactions between the positive and negative electrodes and the electrolyte, the 1C/1C normal-temperature circulation is difficult to reach more than 3500 times, the capacity retention rate is more than or equal to 80%, the 1C/1C45 ℃ high-temperature circulation is difficult to reach more than 2000 times, and the capacity retention rate is more than or equal to 80%. Therefore, the key for improving the cycle performance of the lithium iron phosphate battery is to form a layer of compact protective film on the positive electrode and the negative electrode.
Disclosure of Invention
The invention aims to provide an energy-storage lithium iron phosphate long-life battery electrolyte to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
the lithium iron phosphate long-life battery electrolyte for energy storage comprises a lithium salt, an organic solvent and a synergistic film-forming additive, wherein the concentration of the lithium salt is 0.9-1.2mol/L, and the lithium salt is LiBF4、LiPF6、 LiTFSI、LiAsF6、LiClO4、LiN(SO2C2F5)2The lithium salt accounts for 8-18% of the total mass of the electrolyte.
A lithium iron phosphate long-life battery electrolyte for energy storage is disclosed, and the preparation method of the lithium iron phosphate long-life battery comprises the following steps;
s1: adding an organic solvent into a container at the temperature of-40-0 ℃, adding a lithium salt into the organic solvent, and uniformly mixing to obtain a mixed solution;
s2: and (5) adding a synergistic film forming additive into the mixed solution prepared in the step S1, and uniformly stirring to prepare the lithium iron phosphate long-life battery electrolyte.
As a still further scheme of the invention: the organic solvent is composed of the following materials: 20 to 50 mass percent of cyclic carbonate and 50 to 80 mass percent of chain carbonate.
As a still further scheme of the invention: the cyclic carbonic acid is one of ethylene carbonate, propylene carbonate, gamma-butyrolactone and butylene carbonate, and the chain carbonic acid ester is one or more of dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate.
As a still further scheme of the invention: the synergistic film-forming additive consists of the following materials: the film forming agent comprises a positive CEI film forming agent with the content of 0.1% -0.5%, a negative SEI film forming agent with the content of 1% -3% and a film passivating agent with the content of 0.1% -0.5%, wherein the positive CEI film forming agent is one or more of vinylene carbonate, thiophene, hexamethyldisiloxane and ortho-terphenyl, the negative SEI film forming agent is one or more of ethylene carbonate, vinyl acetate, ethylene sulfite and vinylene carbonate, and the film passivating agent is one or more of lithium bistrifluoromethanesulfonylimide, lithium dioxalate, fluoroethylene carbonate and lithium difluoroborate.
A lithium iron phosphate long-life battery, which comprises a positive plate, a negative plate, a diaphragm and an electrolyte, wherein the electrolyte is the lithium iron phosphate long-life battery electrolyte in any one of the claims 1 and 3.
Compared with the prior art, the invention has the beneficial effects that:
1. in the technical scheme of the invention, in the circulation process of the battery using the electrolyte, a layer of thin and high-strength protective film is formed on the surfaces of the positive and negative pole pieces, so that the occurrence of side reactions between the electrolyte and the pole pieces is reduced, the circulation life of the battery is prolonged, and the performance of the battery is better.
2. On the basis of focusing on a negative electrode SEI film, a positive electrode film forming additive and a film passivation additive are added, so that a layer of compact protective film can be formed on a positive electrode and a negative electrode, the reaction between electrolysis and positive and negative electrode materials is reduced, the cycle performance of a battery core is improved, a thin protective film is generated by using the composite synergistic film forming additive in the cycle process, the side reaction of the positive electrode material and an electrolyte is prevented, the side reaction of the negative electrode and the electrolyte can be reduced by the protective film, the structure of the negative electrode material is prevented from being damaged, and the cycle life is prolonged.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
the lithium iron phosphate long-life battery electrolyte for energy storage comprises a lithium salt, an organic solvent and a synergistic film-forming additive, wherein the concentration of the lithium salt is 0.9mol/L, and the lithium salt is LiBF4、LiPF6、LiTFSI、LiAsF6、 LiClO4、LiN(SO2C2F5)2The lithium salt accounts for 8% of the total mass of the electrolyte, and the synergistic film-forming additive consists of a positive electrode CEI film-forming agent with the content of 0.1%, a negative electrode SEI film-forming agent with the content of 1% and a film passivating agent with the content of 0.1%.
The preparation method of the lithium iron phosphate life battery comprises the following steps;
s1: adding an organic solvent consisting of 20% by mass of propylene carbonate and 50% by mass of ethylene carbonate into a container at the temperature of 0 ℃, adding a lithium salt into the organic solvent, and uniformly mixing to obtain a mixed solution;
s2: and (5) adding a synergistic film forming additive into the mixed solution prepared in the step S1, and uniformly stirring to prepare the lithium iron phosphate long-life battery electrolyte.
A lithium iron phosphate long-life battery comprises a positive plate, a negative plate, a diaphragm and electrolyte.
Example two:
the lithium iron phosphate long-life battery electrolyte for energy storage comprises a lithium salt, an organic solvent and a synergistic film-forming additive, wherein the concentration of the lithium salt is 1.1mol/L, and the lithium salt is LiBF4、LiPF6、LiTFSI、LiAsF6、 LiClO4、LiN(SO2C2F5)2One or more of the above components, lithium salt accounts for 12% of the total mass of the electrolyte, and the synergistic film-forming additive comprises a positive electrode CEI film forming agent with a content of 0.2%, a negative electrode SEI film forming agent with a content of 1.5%, and a film passivating agent with a content of 0.2%.
The preparation method of the lithium iron phosphate life battery comprises the following steps;
s1: adding an organic solvent consisting of 30% by mass of propylene carbonate and 60% by mass of ethylene carbonate into a container at the temperature of-40-0 ℃, adding a lithium salt into the organic solvent, and uniformly mixing to obtain a mixed solution;
s2: and (5) adding a synergistic film forming additive into the mixed solution prepared in the step S1, and uniformly stirring to prepare the lithium iron phosphate long-life battery electrolyte.
A lithium iron phosphate long-life battery comprises a positive plate, a negative plate, a diaphragm and electrolyte.
Example three:
the lithium iron phosphate long-life battery electrolyte for energy storage comprises lithium salt, organic solvent and synergistic film-forming additive, wherein the concentration of the lithium salt1mol/L, and the lithium salt is LiBF4、LiPF6、LiTFSI、LiAsF6、 LiClO4、LiN(SO2C2F5)2One or more of the above components, wherein the lithium salt accounts for 12% of the total mass of the electrolyte, and the synergistic film-forming additive comprises a positive electrode CEI film-forming agent with a content of 0.3%, a negative electrode SEI film-forming agent with a content of 2%, and a film passivating agent with a content of 0.3%.
The preparation method of the lithium iron phosphate life battery comprises the following steps;
s1: adding an organic solvent consisting of 20-50% by mass of propylene carbonate and 50-80% by mass of ethylene carbonate into a container at the temperature of-30 ℃, adding a lithium salt into the organic solvent, and uniformly mixing to obtain a mixed solution;
s2: and (5) adding a synergistic film forming additive into the mixed solution prepared in the step S1, and uniformly stirring to prepare the lithium iron phosphate long-life battery electrolyte.
A lithium iron phosphate long-life battery comprises a positive plate, a negative plate, a diaphragm and electrolyte.
Example four:
the lithium iron phosphate long-life battery electrolyte for energy storage comprises a lithium salt, an organic solvent and a synergistic film-forming additive, wherein the concentration of the lithium salt is 1.1mol/L, and the lithium salt is LiBF4、LiPF6、LiTFSI、LiAsF6、 LiClO4、LiN(SO2C2F5)2One or more of the above components, lithium salt accounts for 15% of the total mass of the electrolyte, and the synergistic film-forming additive comprises a positive electrode CEI film-forming agent with a content of 0.4%, a negative electrode SEI film-forming agent with a content of 2%, and a film passivating agent with a content of 0.4%.
The preparation method of the lithium iron phosphate life battery comprises the following steps;
s1: adding an organic solvent consisting of 40% by mass of propylene carbonate and 70% by mass of ethylene carbonate into a container at the temperature of-35 ℃, adding a lithium salt into the organic solvent, and uniformly mixing to obtain a mixed solution;
s2: and (5) adding a synergistic film forming additive into the mixed solution prepared in the step S1, and uniformly stirring to prepare the lithium iron phosphate long-life battery electrolyte.
A lithium iron phosphate long-life battery comprises a positive plate, a negative plate, a diaphragm and electrolyte.
Example five:
the lithium iron phosphate long-life battery electrolyte for energy storage comprises a lithium salt, an organic solvent and a synergistic film-forming additive, wherein the concentration of the lithium salt is 1.2mol/L, and the lithium salt is LiBF4、LiPF6、LiTFSI、LiAsF6、 LiClO4、LiN(SO2C2F5)2The lithium salt accounts for 18% of the total mass of the electrolyte, and the synergistic film-forming additive consists of a positive electrode CEI film-forming agent with the content of 0.5%, a negative electrode SEI film-forming agent with the content of 3% and a film passivating agent with the content of 0.5%.
The preparation method of the lithium iron phosphate life battery comprises the following steps;
s1: adding an organic solvent consisting of 50% by mass of propylene carbonate and 80% by mass of ethylene carbonate into a container at the temperature of 0 ℃, adding a lithium salt into the organic solvent, and uniformly mixing to obtain a mixed solution;
s2: and (5) adding a synergistic film forming additive into the mixed solution prepared in the step S1, and uniformly stirring to prepare the lithium iron phosphate long-life battery electrolyte.
A lithium iron phosphate long-life battery comprises a positive plate, a negative plate, a diaphragm and electrolyte.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.
Claims (6)
1. A lithium iron phosphate long-life battery electrolyte for energy storage comprises lithiumSalt, organic solvent and synergistic film forming additive, characterized in that: the concentration of the lithium salt is 0.9-1.2mol/L, and the lithium salt is LiBF4、LiPF6、LiTFSI、LiAsF6、LiClO4、LiN(SO2C2F5)2The lithium salt accounts for 8-18% of the total mass of the electrolyte.
2. The lithium iron phosphate long-life battery electrolyte for energy storage as claimed in claim 1, wherein: the preparation method of the lithium iron phosphate life battery comprises the following steps;
s1: adding an organic solvent into a container at the temperature of-40-0 ℃, adding a lithium salt into the organic solvent, and uniformly mixing to obtain a mixed solution;
s2: and (5) adding a synergistic film forming additive into the mixed solution prepared in the step S1, and uniformly stirring to prepare the lithium iron phosphate long-life battery electrolyte.
3. The lithium iron phosphate long-life battery electrolyte for energy storage as claimed in claim 1, wherein: the organic solvent is composed of the following materials: 20 to 50 mass percent of cyclic carbonate and 50 to 80 mass percent of chain carbonate.
4. The lithium iron phosphate long-life battery electrolyte for energy storage according to claim 3, wherein: the cyclic carbonic acid is one of ethylene carbonate, propylene carbonate, gamma-butyrolactone and butylene carbonate, and the chain carbonic acid ester is one or more of dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate.
5. The lithium iron phosphate long-life battery electrolyte for energy storage as claimed in claim 1, wherein: the synergistic film-forming additive consists of the following materials: the film forming agent comprises a positive CEI film forming agent with the content of 0.1% -0.5%, a negative SEI film forming agent with the content of 1% -3% and a film passivating agent with the content of 0.1% -0.5%, wherein the positive CEI film forming agent is one or more of vinylene carbonate, thiophene, hexamethyldisiloxane and ortho-terphenyl, the negative SEI film forming agent is one or more of ethylene carbonate, vinyl acetate, ethylene sulfite and vinylene carbonate, and the film passivating agent is one or more of lithium bistrifluoromethanesulfonylimide, lithium dioxalate, fluoroethylene carbonate and lithium difluoroborate.
6. The utility model provides a lithium iron phosphate long-life battery, includes positive plate, negative pole piece, diaphragm and electrolyte, its characterized in that: the electrolyte is an lithium iron phosphate long-life battery electrolyte as defined in any one of claims 1 and 3.
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| CN201911001395.6A CN111048832A (en) | 2019-10-21 | 2019-10-21 | Lithium iron phosphate long-life battery electrolyte for energy storage |
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| CN201911001395.6A CN111048832A (en) | 2019-10-21 | 2019-10-21 | Lithium iron phosphate long-life battery electrolyte for energy storage |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116154177A (en) * | 2023-04-18 | 2023-05-23 | 蔚来电池科技(安徽)有限公司 | Secondary battery and device |
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Inventor after: Ge Zhimin Inventor after: Shuai Genghong Inventor after: Zhou Wei Inventor after: Tang Jiaojun Inventor after: Xu Liang Inventor after: Pi Yuping Inventor after: Gao Run Inventor after: Nanguang Inventor after: Huang Ming Inventor before: Shuai Genghong Inventor before: Ge Zhimin Inventor before: Zhou Wei Inventor before: Tang Jiaojun Inventor before: Xu Liang Inventor before: Pi Yuping Inventor before: Gao Run Inventor before: Nanguang Inventor before: Huang Ming |
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Address after: No. 2551, sunshine Avenue, high tech Development Zone, Xinyu City, Jiangxi Province Applicant after: Jiangxi Ganfeng lithium Technology Co.,Ltd. Address before: No. 2551, sunshine Avenue, high tech Development Zone, Xinyu City, Jiangxi Province Applicant before: JIANGXI GANFENG BATTERY TECHNOLOGY Co.,Ltd. |
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Application publication date: 20200421 |
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