CN108110230B - Lithium-chromium rechargeable battery and manufacturing method thereof - Google Patents
Lithium-chromium rechargeable battery and manufacturing method thereof Download PDFInfo
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- CN108110230B CN108110230B CN201711199347.3A CN201711199347A CN108110230B CN 108110230 B CN108110230 B CN 108110230B CN 201711199347 A CN201711199347 A CN 201711199347A CN 108110230 B CN108110230 B CN 108110230B
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
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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
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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
- H01M10/058—Construction or manufacture
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a lithium-chromium rechargeable battery and a manufacturing method thereof, the lithium-chromium rechargeable battery comprises a battery anode made of lithium-chromium oxide, a battery cathode made of boron oxide or aluminum-nickel alloy, and a fluorosulfamine organic solution injected into an electrolyte, and on the basis of traditional electron storage, the lithium-chromium oxide in the electrolyte and the boron oxide or the aluminum-nickel alloy are subjected to a synergistic reaction, and the lithium-chromium oxide performs a reversible electrochemical reaction on the surface of the boron oxide or the aluminum-nickel alloy to further store electrons, so that the capacity of the battery is greatly increased, the large-current characteristic of the battery is improved, and the cycle life of the battery is further prolonged.
Description
Technical Field
The invention relates to the field of batteries, in particular to a lithium-chromium rechargeable battery with high energy density, low self-discharge rate and long cycle life and a manufacturing method thereof.
Background
Currently, energy conservation and emission reduction become necessary requirements for the development of economic society in China, and meanwhile, the development of the future society still needs rechargeable batteries with high capacity and long service life for support, and high-capacity batteries are needed in the fields of consumer electronics, electric automobiles, aerospace and the like.
The existing rechargeable nickel-ion battery is a rechargeable battery which takes manganese oxide material as positive active material, takes nickel as negative active material and takes aqueous solution containing nickel ions as electrolyte. A common rechargeable nickel-ion battery uses manganese dioxide as a positive electrode, nickel as a negative electrode, and an aqueous solution containing nickel ions as an electrolyte.
The battery has the characteristics of low price and long cycle life, but the capacity of the battery is too low, is only about 100-300 mAh/g, and has short service life. Therefore, batteries having higher capacities and longer service lives are urgently required.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the defects of the prior art are overcome, and the lithium chromium rechargeable battery and the manufacturing method thereof are provided, wherein the battery has the characteristics of high capacity and long cycle life.
The invention aims to provide a lithium-chromium rechargeable battery, which comprises a battery anode, wherein the material of the battery anode is lithium chromium oxide;
the battery cathode is made of boron oxide or aluminum-nickel alloy;
an electrolyte for soaking the battery positive electrode and the battery negative electrode to cause electrolytic charge and discharge reactions;
the electrolyte comprises propyl sulfate, ethyl sulfate and dimethoxypropane organic solutions with the same percentage, and also comprises at least one of a fluorosulfamine organic solution and a fluorine arsenic imine organic solution.
When the electrolyte does not contain the fluorine arsenic imine organic solution, the content of the fluorine thiamine organic solution is 0.8 mol/L.
When the electrolyte does not contain the fluorosulfamine organic solution, the content of the fluorine arsenic imine organic solution is 1.2 mol/L.
When the electrolyte contains a fluorosulfuric amine organic solution and a fluorine arsenic imine organic solution, the content of the fluorosulfuric amine organic solution is 0.5mol/L, and the content of the fluorine arsenic imine organic solution is 0.9 mol/L.
Wherein, the lithium chromium oxide is externally wrapped with a layer of graphite carbon material.
Meanwhile, the invention also provides a manufacturing method of the lithium-chromium rechargeable battery, which comprises the following steps:
a. manufacturing a battery positive electrode with lithium chromium oxide as an active material;
b. manufacturing a battery cathode taking boron oxide or an aluminum-nickel alloy as an active material;
c. preparing propyl sulfate, ethyl sulfate and dimethoxypropane organic solution in equal ratio as electrolyte base solution, and then adding at least one of fluorosulfuric amine organic solution and fluorine arsenic imine organic solution into the electrolyte base solution to form electrolyte;
d. and packaging the anode, the cathode and the electrolyte to obtain the lithium-chromium rechargeable battery.
When the electrolyte does not contain the fluorine arsenic imine organic solution, the content of the fluorine thiamine organic solution is 0.8 mol/L.
When the electrolyte does not contain the fluorosulfamine organic solution, the content of the fluorine arsenic imine organic solution is 1.2 mol/L.
When the electrolyte contains a fluorosulfuric amine organic solution and a fluorine arsenic imine organic solution, the content of the fluorosulfuric amine organic solution is 0.5mol/L, and the content of the fluorine arsenic imine organic solution is 0.9 mol/L.
In the step a, a layer of graphite carbon material is coated outside the lithium chromium oxide.
According to the lithium-chromium rechargeable battery provided by the invention, the anode material is a lithium-chromium oxide composite material, at least one of a fluorosulfamine organic solution and a fluorine arsenic imine organic solution is injected into the electrolyte, and on the basis of traditional electron storage, the lithium-chromium oxide in the electrolyte is subjected to a synergistic reaction with boron oxide or an aluminum-nickel alloy, and the lithium-chromium oxide performs a reversible electrochemical reaction on the surface of the boron oxide or the aluminum-nickel alloy to further store electrons, so that the capacity of the battery is greatly increased, the large-current characteristic of the battery is improved, and the cycle life of the battery is further prolonged.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic structural view of a lithium-chromium rechargeable battery according to an embodiment of the present invention.
Reference numerals: 1-a battery positive electrode; 2-battery negative electrode; 3-electrolyte.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
A lithium-chromium rechargeable battery according to an embodiment of the present invention, including a battery positive electrode 1, a battery negative electrode 2, and an electrolyte 3, will be described in detail with reference to fig. 1.
Specifically, the material of the battery positive electrode 1 is lithium chromium oxide; the material of the battery cathode 2 is boron oxide or aluminum-nickel alloy; the electrolyte 3 is used for soaking the battery anode 1 and the battery cathode 2 to generate electrolytic charge and discharge reaction; the electrolyte 3 comprises propyl sulfate, ethyl sulfate and dimethoxypropane organic solutions with the same percentage, and also comprises at least one of a fluorosulfamine organic solution and a fluorine arsenic imine organic solution.
In one embodiment, the electrolyte 3 does not contain a fluorine arsenic imine organic solution, and the content of the fluorine thiamine organic solution is 0.8 mol/L.
In another example, the electrolyte 3 does not contain the fluorosulfamine organic solution, and the content of the fluoroarsenimine organic solution is 1.2 mol/L.
In still another example, the electrolyte 3 contains an organic solution of fluorosulfamine and an organic solution of fluoroarsenimine, wherein the content of the organic solution of fluorosulfamine is 0.5mol/L, and the content of the organic solution of fluoroarsenimine is 0.9 mol/L.
And a layer of graphite carbon material is wrapped outside the lithium chromium oxide.
The embodiment of the invention provides a method for manufacturing a lithium-chromium rechargeable battery, which comprises the following specific steps:
a. manufacturing a battery positive electrode with lithium chromium oxide as an active material;
b. manufacturing a battery cathode taking boron oxide or an aluminum-nickel alloy as an active material;
c. preparing propyl sulfate, ethyl sulfate and dimethoxypropane organic solution in equal ratio as electrolyte base solution, and then adding at least one of fluorosulfuric amine organic solution and fluorine arsenic imine organic solution into the electrolyte base solution to form electrolyte;
d. and packaging the anode, the cathode and the electrolyte to obtain the lithium-chromium rechargeable battery.
In one embodiment, in the step c, the electrolyte does not contain a fluorine arsenic imine organic solution, and the content of the fluorine thiamine organic solution is 0.8 mol/L.
In another embodiment, in the step c, the electrolyte does not contain a fluorosulfamine organic solution, and the content of the fluorine arsenic imine organic solution is 1.2 mol/L.
In another embodiment, in the step c, the electrolyte contains an organic solution of fluorosulfuric amine and an organic solution of fluoroarsenimine, the content of the organic solution of fluorosulfuric amine is 0.5mol/L, and the content of the organic solution of fluoroarsenimine is 0.9 mol/L.
In some optional examples, in the step a, a layer of graphitic carbon material is coated outside the lithium chromium oxide.
In the above embodiments of the present invention, the fluorosulfamine organic solution has a lower electrical constant than the fluoroarsenimine organic solution, but the concentration of the electrolyte is not increased, and if the content is too large, it is difficult to obtain a large discharge capacity, so the content is limited within a certain range, and is usually configured to be 0.8 mol/L; when the contents of the organic solution of the fluorosulfuric amine and the organic solution of the fluoroarsenimine are in a specified range, the electrical constant of the electrolyte can be effectively improved, and the discharge capacity of the lithium-chromium rechargeable battery is increased.
Further, since the fluoroarsenimine organic solution has a high viscosity, a low conductivity, and a high melting point, and if the content is too large, the performance may be deteriorated at a low temperature, the content is limited to a certain range, and is usually configured to be 1.2 mol/L.
Furthermore, when the content of the organic solution of fluorosulfuric amine and the organic solution of fluoroarsenifeimine in the electrolyte is kept within a predetermined range, the increase of the internal resistance of the battery in a low-temperature environment can be effectively suppressed, and the capacity can be kept from decreasing in a low-temperature environment.
In summary, according to the lithium-chromium rechargeable battery and the manufacturing method thereof of the present invention, the positive electrode material is a lithium-chromium oxide composite material, and the electrolyte is injected with at least one of the fluorosulfamine organic solution and the fluoroarsenimine organic solution, and on the basis of the conventional electron storage, the lithium-chromium oxide in the electrolyte synergistically reacts with the boron oxide or the aluminum-nickel alloy, and the lithium-chromium oxide performs a reversible electrochemical reaction on the surface of the boron oxide or the aluminum-nickel alloy, thereby further storing electrons, thereby greatly increasing the capacity of the battery, improving the large current characteristic of the battery, and further improving the cycle life of the battery.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. indicate orientations or positional relationships based on those shown in the drawings, and are used merely for convenience of description and for simplicity of description, and do not indicate or imply that the device or element so referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus should not be considered as limiting the present invention.
In the present invention, unless otherwise expressly specified or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (6)
1. A lithium-chromium rechargeable battery, comprising:
the material of the battery positive electrode is lithium chromium oxide;
the battery cathode is made of boron oxide or aluminum-nickel alloy;
an electrolyte for soaking the battery positive electrode and the battery negative electrode to cause electrolytic charge and discharge reactions;
the electrolyte comprises propyl sulfate, ethyl sulfate, dimethoxypropane organic solution and fluorosulfamine organic solution which are the same in percentage.
2. The lithium chromium rechargeable battery according to claim 1, wherein the content of the fluorosulfamine organic solution is 0.8 mol/L.
3. The lithium chromium rechargeable battery according to claim 1 or 2 wherein the lithium chromium oxide is overwrapped with a layer of graphitic carbon material.
4. A method of manufacturing a lithium-chromium rechargeable battery, comprising the steps of:
s1, manufacturing a battery anode taking lithium chromium oxide as an active material;
s2, manufacturing a battery cathode taking boron oxide or aluminum-nickel alloy as an active material;
s3, preparing propyl sulfate, ethyl sulfate and dimethoxypropane organic solutions in equal ratio as electrolyte base liquid, and then adding a fluorosulfuric amine organic solution into the electrolyte base liquid to form electrolyte;
and S4, packaging the anode, the cathode and the electrolyte to obtain the lithium-chromium rechargeable battery.
5. The method according to claim 4, wherein in the step S3, the content of the fluorosulfamine organic solution is 0.8 mol/L.
6. The method of claim 4 or 5, wherein in step S1, a layer of graphitic carbon material is coated on the lithium chromium oxide.
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| CN201711199347.3A CN108110230B (en) | 2017-11-26 | 2017-11-26 | Lithium-chromium rechargeable battery and manufacturing method thereof |
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| CN108110230B true CN108110230B (en) | 2020-06-02 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102110839A (en) * | 2009-12-29 | 2011-06-29 | 万向电动汽车有限公司 | Battery |
| CN104221204A (en) * | 2012-03-26 | 2014-12-17 | 汽车能源供应公司 | Lithium-ion secondary cell |
| JP5691828B2 (en) * | 2011-05-17 | 2015-04-01 | 日本電気株式会社 | Secondary battery |
| CN106450438A (en) * | 2016-10-17 | 2017-02-22 | 广州天赐高新材料股份有限公司 | Lithium-ion battery electrolyte and lithium ion battery with the same |
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- 2017-11-26 CN CN201711199347.3A patent/CN108110230B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102110839A (en) * | 2009-12-29 | 2011-06-29 | 万向电动汽车有限公司 | Battery |
| JP5691828B2 (en) * | 2011-05-17 | 2015-04-01 | 日本電気株式会社 | Secondary battery |
| CN104221204A (en) * | 2012-03-26 | 2014-12-17 | 汽车能源供应公司 | Lithium-ion secondary cell |
| CN106450438A (en) * | 2016-10-17 | 2017-02-22 | 广州天赐高新材料股份有限公司 | Lithium-ion battery electrolyte and lithium ion battery with the same |
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| CN108110230A (en) | 2018-06-01 |
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