CN102610855A - Lithium ferric phosphate battery with improved electrode performance and manufacturing method thereof - Google Patents
Lithium ferric phosphate battery with improved electrode performance and manufacturing method thereof Download PDFInfo
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- CN102610855A CN102610855A CN2012100989857A CN201210098985A CN102610855A CN 102610855 A CN102610855 A CN 102610855A CN 2012100989857 A CN2012100989857 A CN 2012100989857A CN 201210098985 A CN201210098985 A CN 201210098985A CN 102610855 A CN102610855 A CN 102610855A
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- electrode
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- ferric phosphate
- barrier film
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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 ferric phosphate battery with improved electrode performance. The lithium ferric phosphate battery comprises a battery diaphragm, wherein the battery diaphragm comprises an ethylene oxide (EO) group diaphragm; the surface of the EO group diaphragm is grafted with EO groups. The surface of the diaphragm is grafted with EO functional group by a plasma processing method, then the diaphragm grafted with the functional group is assembled with lithium ferric phosphate electrodes to form the battery; because of the modification function of the EO functional group on the surface of the diaphragm, the electrochemical performance of the lithium ferric phosphate electrode can be improved. The lithium ferric phosphate battery disclosed by the invention has the advantages that the battery diaphragm has EO group, and the machining is convenient and is compatible with the machinability, the mechanical performance, the electrical performance and the electrochemical performance of the diaphragm.
Description
Technical field
The present invention relates to the technical field of lithium ion battery, especially a kind of ferric phosphate lithium cell that improves electrode performance and preparation method thereof.
Background technology
Fossil class energy reserve is limited, solution by way of one of be the development and utilization of new forms of energy.New forms of energy comprise tidal energy, wind energy, solar energy, geothermal energy or the like; Their common feature is that Regional Distribution is inhomogeneous, generated output is unstable; Therefore, when utilizing these energy generatings, need an energy accumulating device to link generating and two links of electricity consumption.Energy storage device is main with secondary cell, comprises Ni-MH battery, flow battery, lithium ion battery and lead-acid battery or the like, and wherein lithium ion battery attracts researcher's attention more.
The needs in market and researcher's curiosity are the major impetus that promotes Study on Li-ion batteries using, and people constantly explore the new type lithium ion battery system with performances such as the energy density that improves battery, cycle lives.Wherein, olivine structure lithium iron phosphate LiFePO
4Attract numerous researchers' attention with the discharge platform of its 3.5V, near the specific discharge capacity of 170mAh/g and long circulation life, the low cost of raw material.
Several factors influences LiFePO
4The electrode performance of material, research confirm that this material and electrolyte interface character are vital factors of its electrode performance of decision, and stable electrolyte/electrode interface structure is the prerequisite condition that guarantees its electro-chemical activity.The method of improving this material and electrolyte interface is a lot, as by the method for the widely used carbon coated of numerous researchers.Effect that it is generally acknowledged carbon mainly contains 2 points, and the one, improve electronic conductivity, the 2nd, reduce granular size.Carbon also has negative effect, and too high levels can significantly reduce the electrode capacity of material.Though but the content that does not also have final conclusion it is generally acknowledged carbon is best with about 2%.
In fact, finished product lithium ion battery septation closely contacts with electrode.Therefore, exist the approach of the method improvement electrode performance that utilizes the membrane surface modification.
Summary of the invention
Technical problem to be solved by this invention is to the above-mentioned state of the art, and provides battery diaphragm to contain EO group, easy to process, machinability, mechanical performance and the electrical property of taking into account barrier film and a kind of ferric phosphate lithium cell that improves electrode performance of chemical property and preparation method thereof.
The present invention solves the problems of the technologies described above the technical scheme that is adopted:
A kind of ferric phosphate lithium cell that improves electrode performance comprises battery diaphragm, and wherein, battery diaphragm includes EO group barrier film, and EO group membrane surface is grafted with the EO group.
A kind of manufacture method of improving the ferric phosphate lithium cell of electrode performance, wherein,
May further comprise the steps:
Step 1; Adopting electric glow discharge method to use the Cement Composite Treated by Plasma appearance to carry out power the electrode diaphragm of clean dry is that 5 watts to 10 watts, time are 10 minutes to 30 minutes Cement Composite Treated by Plasma; And the coil distance of electrode diaphragm and Cement Composite Treated by Plasma appearance is 8 centimetres to 10 centimetres; Processing atmosphere is EO, and gas flow is 20 milliliters of per minutes; Back acquisition EO group barrier film disposes;
Step 2; Be negative pole with the lithium metal, with EO group barrier film or EO group barrier film and electrode diaphragm combination as battery diaphragm, be positive pole, be electrolyte with the lithium hexafluoro phosphate organic solution of 1mol/L with the LiFePO4 electrode, be assembled into the ferric phosphate lithium cell of improvement electrode performance successively by the order of lithium metal, battery diaphragm, LiFePO4 electrode.
The present invention solves the problems of the technologies described above the technical scheme that is adopted:
Electrode diaphragm is polyethylene barrier film or polypropylene diaphragm or polyethylene and polypropylene mixing barrier film in the step 1.
Pressure when electrode diaphragm is handled through the Cement Composite Treated by Plasma appearance in the step 1 is 30Pa to 50Pa.
Organic solvent in the step 2 in the lithium hexafluoro phosphate organic solution is that volume ratio is ethylene carbonate and the diethyl carbonate of 1:1.
Organic solvent in the step 2 in the lithium hexafluoro phosphate organic solution is that volume ratio is ethylene carbonate and the propene carbonate of 1:1.
The LiFePO4 electrode is carbon-free pure LiFePO4 electrode or LiFePO4/C combination electrode in the step 2.
Compared with prior art, a kind of ferric phosphate lithium cell that improves electrode performance of the present invention comprises battery diaphragm, and wherein, battery diaphragm includes EO group barrier film, and EO group membrane surface is grafted with the EO group.The manufacture method of this ferric phosphate lithium cell may further comprise the steps: step 1; Adopting electric glow discharge method to use the Cement Composite Treated by Plasma appearance to carry out power the electrode diaphragm of clean dry is that 5 watts to 10 watts, time are 10 minutes to 30 minutes Cement Composite Treated by Plasma; And the coil distance of electrode diaphragm and Cement Composite Treated by Plasma appearance is 8 centimetres to 10 centimetres; Processing atmosphere is EO, and gas flow is 20 milliliters of per minutes; Back acquisition EO group barrier film disposes;
Step 2; Be negative pole with the lithium metal, with EO group barrier film or EO group barrier film and electrode diaphragm combination as battery diaphragm, be positive pole, be electrolyte with the lithium hexafluoro phosphate organic solution of 1mol/L with the LiFePO4 electrode, be assembled into the ferric phosphate lithium cell of improvement electrode performance successively by the order of lithium metal, battery diaphragm, LiFePO4 electrode.EO is an oxirane.Method EO functional group in the membrane surface grafting through Cement Composite Treated by Plasma; Again with grafting the barrier film and the LiFePO4 electrode of this functional group be assembled into battery; Because the modification of membrane surface EO functional group, thereby the chemical property of improvement LiFePO4 electrode.The invention has the advantages that: do not need to process again, prepare the novel barrier film that contains the EO group, only need be on existing commercialization membrane surface modify and graft the EO group just passable.Overcome the shortcoming in the research and development of new types of diaphragm, for example will take into account machinability, mechanical performance and the electrical property of barrier film and the shortcoming of chemical property.At existing commercialization membrane surface grafting EO group, on the basis of the mechanical strength that does not influence protocnemes basically, thickness, directly develop multifunctional membrane.
Embodiment
Below embodiments of the invention are described in further detail.
First embodiment:
Polypropylene diaphragm is cleaned up; It is 30 minutes Cement Composite Treated by Plasma as 5W, time that dry back adopts the method for glow discharge to use the Cement Composite Treated by Plasma appearance to carry out power; The coil distance 8cm of barrier film and Cement Composite Treated by Plasma appearance; Processing atmosphere is EO, and gas flow is 20mL/ minute, and pressure is 30Pa; Back acquisition EO group barrier film disposes.
With the lithium metal is negative pole; With the LiFePO4/C combination electrode is positive pole; With EO group barrier film is battery diaphragm; Lithium hexafluoro phosphate organic solution with 1mol/L is electrolyte, is assembled into the ferric phosphate lithium cell of improvement electrode performance successively by the order of lithium metal, battery diaphragm, LiFePO4/C combination electrode.Organic solvent in the lithium hexafluoro phosphate organic solution is that volume ratio is ethylene carbonate and the diethyl carbonate of 1:1.The constant current charge-discharge result confirms, 0.1C multiplying power bottom electrode capacity is 120mAh/g when using untreated original barrier film, use the barrier film of handling after capacity reach 130mAh/g.
Second embodiment:
The polyethylene barrier film is cleaned up, dry back adopt the method for glow discharge use the Cement Composite Treated by Plasma appearance power as the 10W condition under Cement Composite Treated by Plasma barrier film 10 minutes, the coil distance 10cm of barrier film and Cement Composite Treated by Plasma appearance; Barrier film one side covering protection barrier film, opposite side be towards the coil of Cement Composite Treated by Plasma appearance, earlier with oxygen treatments applied 5 minutes; Then turn off oxygen; Handle atmosphere and change EO into, gas flow is 20mL/ minute, and pressure is 50Pa.Processing finishes the back and uses the absolute ethyl alcohol cleaning membrane, and 50 ℃ of dryings of final vacuum; Back acquisition EO group barrier film disposes.
With the lithium metal is negative pole; With the LiFePO4/C combination electrode is positive pole; Be combined as battery diaphragm with EO group barrier film and electrode diaphragm; Lithium hexafluoro phosphate organic solution with 1mol/L is electrolyte, is assembled into the ferric phosphate lithium cell of improvement electrode performance successively by the order of lithium metal, battery diaphragm, LiFePO4/C combination electrode.Organic solvent in the lithium hexafluoro phosphate organic solution is that volume ratio is ethylene carbonate and the propene carbonate of 1:1.The constant current charge-discharge result confirms, 0.1C multiplying power bottom electrode capacity is 135mAh/g when using untreated original barrier film, use the barrier film of handling after capacity reach 150mAh/g.
The 3rd embodiment:
The polyethylene of commercialization sandwich construction is cleaned up with polypropylene mixing barrier film, dry back adopt the method for glow discharge use the Cement Composite Treated by Plasma appearance power as the 10W condition under Cement Composite Treated by Plasma barrier film 10 minutes, the coil distance 10cm of barrier film and Cement Composite Treated by Plasma appearance; Barrier film one side covering protection barrier film, opposite side be towards the coil of Cement Composite Treated by Plasma appearance, earlier with oxygen treatments applied 5 minutes; Then turn off oxygen; Handle atmosphere and change EO into, gas flow is 20mL/ minute, and pressure is 50Pa.Processing finishes the back and uses the absolute ethyl alcohol cleaning membrane, and 50 ℃ of dryings of final vacuum; Back acquisition EO group barrier film disposes.
With the lithium metal is negative pole; With carbon-free pure LiFePO4 electrode is positive pole; Be combined as battery diaphragm with EO group barrier film and electrode diaphragm; Lithium hexafluoro phosphate organic solution with 1mol/L is electrolyte, is assembled into the ferric phosphate lithium cell of improvement electrode performance successively by the order of lithium metal, battery diaphragm, carbon-free pure LiFePO4 electrode.Organic solvent in the lithium hexafluoro phosphate organic solution is that volume ratio is ethylene carbonate and the propene carbonate of 1:1.The constant current charge-discharge result confirms, 0.1C multiplying power bottom electrode capacity is 35mAh/g when using untreated original barrier film, use the barrier film of handling after capacity reach 45mAh/g.
Method EO functional group in the membrane surface grafting through Cement Composite Treated by Plasma; Again with grafting the barrier film and the LiFePO4 electrode of this functional group be assembled into battery; Because the modification of membrane surface EO functional group, thereby the chemical property of improvement LiFePO4 electrode.
The invention has the advantages that: do not need to process again, prepare the novel barrier film that contains the EO group, only need be on existing commercialization membrane surface modify and graft the EO group just passable.Overcome the shortcoming in the research and development of new types of diaphragm, for example will take into account machinability, mechanical performance and the electrical property of barrier film and the shortcoming of chemical property.At existing commercialization membrane surface grafting EO group, on the basis of the mechanical strength that does not influence protocnemes basically, thickness, directly develop multifunctional membrane.
Claims (7)
1. a ferric phosphate lithium cell that improves electrode performance comprises battery diaphragm, it is characterized in that: described battery diaphragm includes EO group barrier film, and described EO group membrane surface is grafted with the EO group.
2. the manufacture method of the ferric phosphate lithium cell of an improvement electrode performance as claimed in claim 1 is characterized in that:
May further comprise the steps:
Step 1; Adopting electric glow discharge method to use the Cement Composite Treated by Plasma appearance to carry out power the electrode diaphragm of clean dry is that 5 watts to 10 watts, time are 10 minutes to 30 minutes Cement Composite Treated by Plasma; And the coil distance of described electrode diaphragm and Cement Composite Treated by Plasma appearance is 8 centimetres to 10 centimetres; Processing atmosphere is EO, and gas flow is 20 milliliters of per minutes; Back acquisition EO group barrier film disposes;
Step 2; Be negative pole with the lithium metal, with EO group barrier film or EO group barrier film and the combination of described electrode diaphragm as battery diaphragm, be positive pole, be electrolyte with the lithium hexafluoro phosphate organic solution of 1mol/L with the LiFePO4 electrode, be assembled into the ferric phosphate lithium cell of improvement electrode performance successively by the order of lithium metal, battery diaphragm, LiFePO4 electrode.
3. a kind of manufacture method of improving the ferric phosphate lithium cell of electrode performance according to claim 2 is characterized in that: electrode diaphragm is polyethylene barrier film or polypropylene diaphragm or polyethylene and polypropylene mixing barrier film in the described step 1.
4. a kind of manufacture method of improving the ferric phosphate lithium cell of electrode performance according to claim 2 is characterized in that: the pressure when electrode diaphragm is handled through the Cement Composite Treated by Plasma appearance in the described step 1 is 30Pa to 50Pa.
5. a kind of manufacture method of improving the ferric phosphate lithium cell of electrode performance according to claim 2 is characterized in that: the organic solvent in the described step 2 in the lithium hexafluoro phosphate organic solution is that volume ratio is ethylene carbonate and the diethyl carbonate of 1:1.
6. a kind of manufacture method of improving the ferric phosphate lithium cell of electrode performance according to claim 2 is characterized in that: the organic solvent in the described step 2 in the lithium hexafluoro phosphate organic solution is that volume ratio is ethylene carbonate and the propene carbonate of 1:1.
7. a kind of manufacture method of improving the ferric phosphate lithium cell of electrode performance according to claim 2 is characterized in that: the LiFePO4 electrode is carbon-free pure LiFePO4 electrode or LiFePO4/C combination electrode in the described step 2.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012100989857A CN102610855A (en) | 2012-04-06 | 2012-04-06 | Lithium ferric phosphate battery with improved electrode performance and manufacturing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012100989857A CN102610855A (en) | 2012-04-06 | 2012-04-06 | Lithium ferric phosphate battery with improved electrode performance and manufacturing method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108701848A (en) * | 2016-02-03 | 2018-10-23 | 住友电气工业株式会社 | Redox flow batteries |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5270137A (en) * | 1991-09-18 | 1993-12-14 | Fuji Photo Film Co., Ltd. | Secondary battery with graft-polymerized separator |
| CN101252175A (en) * | 2008-03-13 | 2008-08-27 | 深圳市富易达电子科技有限公司 | Method for modifying nonwoven polypropylene for battery diaphragm |
| CN102054953A (en) * | 2010-12-10 | 2011-05-11 | 苏州大学 | Processing method of septum for secondary lithium battery as well as secondary lithium battery |
-
2012
- 2012-04-06 CN CN2012100989857A patent/CN102610855A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5270137A (en) * | 1991-09-18 | 1993-12-14 | Fuji Photo Film Co., Ltd. | Secondary battery with graft-polymerized separator |
| CN101252175A (en) * | 2008-03-13 | 2008-08-27 | 深圳市富易达电子科技有限公司 | Method for modifying nonwoven polypropylene for battery diaphragm |
| CN102054953A (en) * | 2010-12-10 | 2011-05-11 | 苏州大学 | Processing method of septum for secondary lithium battery as well as secondary lithium battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108701848A (en) * | 2016-02-03 | 2018-10-23 | 住友电气工业株式会社 | Redox flow batteries |
| CN108701848B (en) * | 2016-02-03 | 2021-05-07 | 住友电气工业株式会社 | Redox flow battery |
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Application publication date: 20120725 |