CN102195099A - Method for enhancing stability of LiMnO secondary lithium ion battery - Google Patents
Method for enhancing stability of LiMnO secondary lithium ion battery Download PDFInfo
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- CN102195099A CN102195099A CN201010128558XA CN201010128558A CN102195099A CN 102195099 A CN102195099 A CN 102195099A CN 201010128558X A CN201010128558X A CN 201010128558XA CN 201010128558 A CN201010128558 A CN 201010128558A CN 102195099 A CN102195099 A CN 102195099A
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- 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
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Abstract
The invention discloses a method for enhancing the stability of a LiMnO secondary lithium ion battery. The method comprises a step of: storing the LiMnO secondary lithium ion battery under the condition that the charging depth is 50 to 70 percent of system on chip (SOC) or the storage voltage is 3.95 to 4.05V. In the method, the LiMnO secondary lithium ion battery is stored under a specific condition, so the stability of the LiMnO secondary lithium ion battery can be enhanced, and the capacitance attenuation of the LiMnO battery can be restrained to a certain extent.
Description
Technical field
The present invention relates to a kind of field of lithium ion secondary, particularly relate to a kind of method that can improve LiMn2O4 secondary lithium battery stability.
Background technology
Lithium ion battery has that energy density height, specific power are big, good cycle, memory-less effect, characteristics such as pollution-free, lithium ion battery is widely used in various electronic products such as mobile phone, mobile phone, video camera, notebook computer, simultaneously, lithium ion battery also is the ideal selection of the energy of following electric motor car.The used positive electrode of present business-like lithium ion battery almost is a cobalt acid lithium, but cobalt resource lacks, so there are shortcomings such as cost height, resource-constrained in this material of cobalt acid lithium.Want the sustainable development lithium ion battery, the positive electrode abundant, cheapness of fine quality of need further exploiting natural resources.Because LiMn2O4 has characteristics such as aboundresources, little, the easy recovery of toxicity, voltage platform height, become the positive electrode that is hopeful to replace cobalt acid lithium most.And influence the business-like major obstacle of manganate cathode material for lithium at present be: the electrochemical specific capacity of LiMn2O4 under hot environment reduces rapidly, causes the long-time back capacity that stores to reduce, and cycle performance worsens.The expert is to the explanation of LiMn2O4 capacity attenuation phenomenon both at home and abroad at present, and relatively more consistent saying is: 1) minor amount of water that contains in the electrolyte and electrolyte LiPF
6Reaction, the HF of generation makes the Mn of LiMn2O4 as catalyst
3+Disproportionated reaction takes place generate Mn
4+And Mn
2+, cause the dissolving of manganese; 2) formation of passivating film causes the increase of electrode polarization resistance; 3) the Jahn-Teller effect that takes place during deep discharge causes the variation of lattice structure to make the recycle ratio capacity reduce.For improving the problem of capacity attenuation, brainstrust proposes and the improvement method of having carried out big quantity research roughly has two class directions: 1) internal structure of LiMn2O4 spinelle is modified; 2) surface of positive electrode is modified, promptly used the Mn of some compounds and material surface
2+The dissolving loss of Mn is controlled in complexing.But these two class methods are more complicated all.
Summary of the invention
The objective of the invention is the problems referred to above, provide a kind of and can improve the stability of LiMn2O4 secondary lithium battery, suppress the method for lithium manganate cell volume decay to a certain extent at prior art.
For achieving the above object, the present invention has adopted following technical scheme:
The invention discloses a kind of method that improves LiMn2O4 secondary lithium battery stability, described method comprises the LiMn2O4 secondary lithium battery under the depth of charge condition of 50%SOC-70%SOC, perhaps stores under the stored voltage condition of 3.95-4.05V.
In the preferred embodiment of the present invention, described method comprises the LiMn2O4 secondary lithium battery under the depth of charge condition of 60%SOC, perhaps stores under the stored voltage condition of 4.0V.
In the concrete execution mode of the present invention, the positive active material of described LiMn2O4 secondary lithium battery is a lithium manganate having spinel structure; Negative electrode active material comprises at least a in native graphite, Delanium, the carbonaceous mesophase spherules; In the electrolyte, lithium salts comprises LiPF
6, solvent comprises at least two kinds among EC, PC, EMC, DEC, the DMC; Barrier film is individual layer PE barrier film or three layers of PP/PE/PP barrier film.
Owing to adopted above technical scheme, the beneficial effect that the present invention is possessed is:
Thinking uniqueness of the present invention, proposition is in order to improve the stability of lithium manganate battery, not only can be by material internal or surface are modified, simultaneously also can be by optimizing the storing state of lithium manganate battery, adopt the storage mode of specified conditions, reduce its capacity attenuation, reach the purpose that improves stability test.The present invention stores the LiMn2O4 secondary lithium battery by selecting specified conditions for use, can improve the stability of LiMn2O4 secondary lithium battery, suppress lithium manganate cell volume decay to a certain extent.
Description of drawings
But Fig. 1 is the capacity recovery rate resolution chart result of lithium manganate battery normal temperature storage after 1 month of an embodiment of the present invention;
But Fig. 2 is the capacity recovery rate test result figure of lithium manganate battery normal temperature storage after 3 months of an embodiment of the present invention;
But Fig. 3 is the capacity recovery rate test result figure of lithium manganate battery normal temperature storage after 3 months of an embodiment of the present invention.
Embodiment
At present, in the lithium ion battery industry, the normal storage voltage of electric core (cell) generally is defined as 3.80V-3.90V, the stored voltage of the battery of mobile phone (battery) of finished product is generally 3.75V-3.85V.
But all kinds of positive electrodes that lithium-ion electric core is used are all different as the working voltage platform of cobalt acid lithium, LiMn2O4, nickle cobalt lithium manganate, LiFePO4 etc., therefore store under different voltage statuss, and the stability of its chemical property is also different.
The present invention is that the storing state of the lithium rechargeable battery of LiMn2O4 is studied to positive active material, and existence is than big-difference between the best storing state of finding the LiMn2O4 secondary lithium battery and the commercialization cobalt acid lithium secondary lithium battery for a long time.The present invention proposes a kind of storage method, can effectively suppress the capacity attenuation problem of lithium manganate battery to a certain extent, improve the stability of lithium manganate battery at the LiMn2O4 secondary lithium battery.In the present invention, the best storing state of LiMn2O4 secondary lithium battery is the depth of charge of 50%SOC-70%SOC, and promptly voltage status is 3.95-4.05V; Most preferably be 60% depth of charge, promptly voltage status is 4.00V.
In the concrete execution mode of the present invention, the positive active material of LiMn2O4 secondary lithium battery is a lithium manganate having spinel structure, and its general chemical formula is LiMn
2O
4Negative electrode active material comprises general native graphite and negative materials such as Delanium and carbonaceous mesophase spherules in the lithium ion battery industry; Electrolyte, its lithium salts component is LiPF
6Its solvent composition is made up of two or more of EC (ethylene carbonate), PC (propene carbonate), EMC (methyl ethyl carbonate fat), DEC (carbonic acid diethyl ester), DMC (dimethyl carbonate), the ratio of each solvent can be normally used solvent ratios such as EC/EMC=3/7 in the industry, EC/EMC/DEC=1: 1: 1 or the like; Used diaphragm paper is individual layer PE or three layers of PP/PE/PP barrier film of being used always in the industry.
In conjunction with the accompanying drawings the present invention is described in further detail below by embodiment.
Embodiment:
The production technology of the LiMn2O4 secondary lithium battery of this embodiment is the production technology of conventional LiMn2O4 secondary lithium battery, and is specific as follows:
Positive active material (LiMn2O4), binding agent PVDF (poly-inclined to one side tetrafluoroethene), conductive agent SP are mixed, add solvent NMP (N-methyl arsenic pyrrolidone) then and evenly stir, form anode sizing agent.Made anode sizing agent is coated on aluminium foil two-sided of 16 μ m, dry and roll-in forms positive plate;
Negative electrode active material and conductive agent SFG-6 are mixed, be dispersed in then in CMC (sodium carboxymethylcellulose) aqueous solution that configures, and SBR (butadiene-styrene rubber) added wherein as binding agent, evenly stir the back and form cathode size, made cathode size is uniformly coated on 10 μ m Copper Foils two-sided, and dry and roll-in forms negative plate;
Positive plate and negative plate are cut into the anodal small pieces and the negative pole small pieces of conventional width and length, and welding aluminium strip and nickel strap on anodal small pieces and the negative pole small pieces respectively, afterwards, reel with diaphragm paper and to form the volume core, the volume core is packed in the square aluminum metal shell of suitable dimension, and after shell and block carried out welded seal, inject the electrolyte in the aluminum hull, the electrolyte solvent component that present embodiment adopts is EC/PC/DEC=30/5/55,1M LiPF6 electrolyte, electric core is carried out precharge, after sealing, be made into 053048A-500mAh LiMn2O4 secondary lithium battery.
After with 500mA (1C multiplying power) electric current battery being carried out charge and discharge cycles, with 500mA (1C multiplying power) electric current constant current charge to different depth of charge 20%SOC, 30%SOC, 40%SOC, 50%SOC, 60%SOC, 70%SOC, 80%SOC, 90%SOC, 100%SOC, battery is placed on respectively in the normal temperature stores 1 month, store 3 months in the normal temperature and 60 ℃ of high temperature in store 7 days, investigate the situation of change of the capacity before and after the battery storage.
The LiMn2O4 secondary lithium battery stores the volume change of front and back battery as shown in following table 1,
Capacity restoration rate before and after table 1 lithium manganate battery stores
| The experiment sequence number | Different depth of charge | Stored voltage/V after the charging | But normal temperature storage is the capacity recovery rate after 1 month | But normal temperature storage is the capacity recovery rate after 3 months | But 60 ℃ of storages of high temperature capacity recovery rate after 7 days |
| 1 | 20％SOC | 3.80 | 92.4％ | 92.0％ | 81.7％ |
| 2 | 30％SOC | 3.87 | 94.0％ | 93.1％ | 84.3％ |
| 3 | 40％SOC | 3.90 | 94.8％ | 94.3％ | 86.6％ |
| 4 | 50％SOC | 3.95 | 95.7％ | 94.8％ | 90.7％ |
| 5 | 60％SOC | 4.00 | 96.4％ | 95.3％ | 91.8％ |
| 6 | 70％SOC | 4.05 | 95.4％ | 94.3％ | 90.3％ |
| 7 | 80％SOC | 4.07 | 95.3％ | 94.2％ | 89.2％ |
| 8 | 90％SOC | 4.16 | 95.0％ | 93.7％ | 88.3％ |
| 9 | 100％SOC | 4.19 | 94.7％ | 93.2％ | 86.6％ |
| Maximum | 4.19 | 96.4％ | 92.0％ | 91.8％ | |
| Minimum value | 3.80 | 92.4％ | 95.3％ | 81.7％ |
The lithium manganate battery of different depth of charge, after under normal temperature condition, storing 1 month, but expression in the recovery rate of its capacity such as the accompanying drawing 1, store 1 month under the depth of charge of battery at 50%SOC-70%SOC, but its capacity recovery rate is higher, peak is 60%SOC, the capacity restoration rate reaches 96.4%, that is to say that lithium manganate battery is to store under 60% state at depth of charge, its chemical property is the most stable.
The lithium manganate battery of different depth of charge, after under normal temperature condition, storing 3 months, but expression in the recovery rate of its capacity such as the accompanying drawing 2, store 3 months under the depth of charge of battery at 50%SOC-70%SOC, but its capacity recovery rate is higher, peak is 60%SOC, the capacity restoration rate reaches 95.3%, that is to say that lithium manganate battery is to store under 60% state at depth of charge, its chemical property is the most stable.
The lithium manganate battery of different depth of charge, after 60 ℃ of high temperature store 7 days, but expression in the recovery rate of its capacity such as the accompanying drawing 3, store 7 days under the depth of charge of battery at 50%SOC-70%SOC, but its capacity recovery rate is higher, peak is 60%SOC, the capacity restoration rate reaches 91.8%, that is to say that lithium manganate battery is to store under 60% state at depth of charge, its chemical property is the most stable.
No matter can draw from above statement, be in normal temperature environment or hot environment, but the capacity recovery rate of lithium manganate battery after storage higher be experiment sequence number 4,5,6, and the highest be experiment sequence number 5.Prove that thus the present invention adopts the depth of charge of lithium manganate battery at 50%SOC-70%SOC, be that voltage status is 3.95-4.05V, most preferably be 60% depth of charge, promptly voltage status is to store under the condition of 4.00V, can improve the stability of lithium manganate battery, the reduced capacity decay.
Can draw simultaneously, the best storing state of lithium manganate battery and business-like cobalt acid lithium ion battery differ greatly, and lithium manganate battery shows comparatively stable between 3.95-4.05V, and it is the most stable most preferably to be the 4.00V performance.Therefore, after producing manganate lithium ion battery, the cobalt acid lithium battery that its stored voltage is more general will improve.
Above content be in conjunction with concrete execution mode to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (6)
1. method that improves LiMn2O4 secondary lithium battery stability, it is characterized in that: described method comprises the LiMn2O4 secondary lithium battery under the depth of charge condition of 50%SOC-70%SOC, perhaps stores under the stored voltage condition of 3.95-4.05V.
2. method according to claim 1 is characterized in that: described method comprises the LiMn2O4 secondary lithium battery under the depth of charge condition of 60%SOC, perhaps stores under the stored voltage condition of 4.0V.
3. method according to claim 1 and 2 is characterized in that: the positive active material of described LiMn2O4 secondary lithium battery is a lithium manganate having spinel structure.
4. method according to claim 1 and 2 is characterized in that: the negative electrode active material of described LiMn2O4 secondary lithium battery comprises at least a in native graphite, Delanium, the carbonaceous mesophase spherules.
5. method according to claim 1 and 2 is characterized in that: in the electrolyte of described LiMn2O4 secondary lithium battery, lithium salts comprises LiPF
6, solvent comprises at least two kinds among EC, PC, EMC, DEC, the DMC.
6. method as claimed in claim 1 or 2 is characterized in that: the barrier film of described LiMn2O4 secondary lithium battery is individual layer PE barrier film or three layers of PP/PE/PP barrier film.
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| CN201010128558XA CN102195099A (en) | 2010-03-19 | 2010-03-19 | Method for enhancing stability of LiMnO secondary lithium ion battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103457002A (en) * | 2012-05-28 | 2013-12-18 | 广州丰江电池新技术股份有限公司 | Lithium ion battery storage or transportation method |
| CN109728370A (en) * | 2018-12-25 | 2019-05-07 | 惠州市纬世新能源有限公司 | A kind of storage method improving lithium battery performance |
| CN111384458A (en) * | 2019-12-25 | 2020-07-07 | 南通硬派锂电池有限公司 | Method for inhibiting capacity attenuation of lithium manganate lithium ion battery |
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| CN101154751A (en) * | 2006-09-30 | 2008-04-02 | 万向电动汽车有限公司 | Lithium ion battery and method for effectively restraining capacitance loss of Lithium manganite anode material |
| CN101262062A (en) * | 2008-04-18 | 2008-09-10 | 深圳市崧鼎实业有限公司 | A lithium ion battery cathode material composition, cathode, battery and method |
| CN101504995A (en) * | 2009-02-11 | 2009-08-12 | 中信国安盟固利新能源科技有限公司 | Method for enhancing stability and cycling performance of potassium manganate lithium ion battery |
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2010
- 2010-03-19 CN CN201010128558XA patent/CN102195099A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101154751A (en) * | 2006-09-30 | 2008-04-02 | 万向电动汽车有限公司 | Lithium ion battery and method for effectively restraining capacitance loss of Lithium manganite anode material |
| CN101262062A (en) * | 2008-04-18 | 2008-09-10 | 深圳市崧鼎实业有限公司 | A lithium ion battery cathode material composition, cathode, battery and method |
| CN101504995A (en) * | 2009-02-11 | 2009-08-12 | 中信国安盟固利新能源科技有限公司 | Method for enhancing stability and cycling performance of potassium manganate lithium ion battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103457002A (en) * | 2012-05-28 | 2013-12-18 | 广州丰江电池新技术股份有限公司 | Lithium ion battery storage or transportation method |
| CN109728370A (en) * | 2018-12-25 | 2019-05-07 | 惠州市纬世新能源有限公司 | A kind of storage method improving lithium battery performance |
| CN111384458A (en) * | 2019-12-25 | 2020-07-07 | 南通硬派锂电池有限公司 | Method for inhibiting capacity attenuation of lithium manganate lithium ion battery |
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