CN101279768A - Hybridization method of lithium salt and electrolytic manganese dioxide, application thereof to lithium battery - Google Patents
Hybridization method of lithium salt and electrolytic manganese dioxide, application thereof to lithium battery Download PDFInfo
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- CN101279768A CN101279768A CNA200810301843XA CN200810301843A CN101279768A CN 101279768 A CN101279768 A CN 101279768A CN A200810301843X A CNA200810301843X A CN A200810301843XA CN 200810301843 A CN200810301843 A CN 200810301843A CN 101279768 A CN101279768 A CN 101279768A
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- manganese dioxide
- lithium
- electrolytic manganese
- hydridization
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a lithium salt hybridization electrolytic manganese dioxide and a method for the production thereof and the application in a lithium cell. The lithium salt hybridization electrolytic manganese dioxide is made by evenly mixing a lithium-bearing inorganic compound with a Gamma type electrolytic manganese dioxide present in a mole ratio of Li: Mn is between 1: 11.0 and 12.0, burning the mixture for six to ten hours at a temperature of between 360 to 380 DEG C and cooling the mixture to the room temperature naturally, thereby realizing the hybridization between the lithium salt and the electrolytic manganese dioxide and changing the Gamma type electrolytic manganese dioxide into a Gamma-Beta mixed electrolytic manganese dioxide. A cell electrode flake and a lithium/manganese dioxide cell produced by the lithium salt hybridization electrolytic manganese dioxide of the invention can obviously improve the low temperature discharge performance of the cell, and has higher normal temperature discharge capacity than the lithium/manganese dioxide cell made by the manganese dioxide not undergoing lithium salt hybridization and electrolysis, and has excellent performance under operating conditions of discharge at high rate and low temperature.
Description
Technical field
The present invention relates to a kind of lithium salts hydridization electrolytic manganese dioxide and preparation method thereof, with and application in lithium cell.
Background technology
Lithium/manganese dioxide battery is anode with the metallic lithium, and cathode active material is the electrolytic manganese dioxide powder through special thermal treatment.General electrolytic manganese dioxide (EMD) or chemical manganese bioxide (CMD) contain considerable α and γ type Manganse Dioxide and a spot of crystal water and planar water, and the electrolytic manganese dioxide that the most suitable Manganse Dioxide of making lithium/manganese dioxide battery negative electrode is γ-β mixed type.Therefore, international lithium cell industry adopts method for calcinating dehydration usually, and α and γ type Manganse Dioxide is changed into the Manganse Dioxide of γ β mixed type.Method for calcinating generally uses the hot blast High Temperature Furnaces Heating Apparatus, about 370 ℃ of control furnace temperature temperature, and constant temperature 6-8 hour, naturally cooling can obtain the Manganse Dioxide of γ-β mixed type.
Proof is added lithium ion in the electrolytic manganese dioxide negative electrode by experiment, can reduce the influence of sodium ion, improves the loaded work piece voltage of lithium/manganese dioxide battery, increases the storage life of lithium/manganese dioxide battery.Patent CN1446180A discloses " Mechanochemical synthesis of lithiated manganese dioxide ".According to this method, need electrolytic manganese dioxide and lithium salts mixture are carried out ball milling, promptly " exist under the grinding medium situation, the mixture of the substantially dry of Manganse Dioxide and lithium salts is being carried out mechanical activating technique ", and then carrying out the conversion operation of γ-β mixed type Manganse Dioxide.But ball-milling technology will inevitably make the crystalline network of Manganse Dioxide produce variation, causes the chemical property of anticathode active substance to cause disadvantageous effect.Patent CN118909A discloses " a kind of improved Manganse Dioxide that is used for lithium cell ", need electrolytic manganese dioxide is carried out acidification, with the sodium ion in the hydrogen replacement electrolytic manganese dioxide, " then with containing lithium compound; as the neutralize acid Manganse Dioxide of generation of the basic solution of lithium hydroxide ", " wash this Manganse Dioxide then in a usual manner with water; drying, thermal treatment at high temperature makes γ type Manganse Dioxide change the mixture of γ and beta form into ".Material is taken a lot of work, taken to the electrolytic manganese dioxide that adopts this method to produce, and three waste discharge is more, and its material surface will inevitably residual a small amount of sulfate radical (SO simultaneously
4 2-), although adopt alkali lye neutralization, pure water to clean subsequently, in neutralization, the technological process of cleaning inevitably with relevant positively charged ion, as the Na among the NaOH
+, Ca (OH)
2In Ca
2-, NH
4NH among the OH
4 +, be adsorbed on the surface of electrolytic manganese dioxide.When this electrolytic manganese dioxide is used as lithium/Manganse Dioxide (Li/MnO
2) during the cell cathode active substance, this ion that is adsorbed in the surface of electrolytic manganese dioxide can be released by the discharge of battery, and exchange with lithium in the battery electrolyte, thereby make metallic lithium produce loss as galvanic anode.
In sum, present lithium/manganese dioxide battery pole piece complex manufacturing technology, and the battery plate chemical property that obtains is relatively poor.
Summary of the invention
First technical problem to be solved by this invention provides a kind of lithium salts hydridization electrolytic manganese dioxide.
Lithium salts hydridization electrolytic manganese dioxide of the present invention is by containing lithium mineral compound and γ type electrolytic manganese dioxide with Li: Mn=1: 11.0～12.0 mixed in molar ratio is even, in 360～380 ℃ of calcining 6～10h, naturally cools to room temperature and makes.
The described lithium mineral compound that contains is at least a in Quilonum Retard, lithium fluoride, the lithium hydroxide.
Described γ type electrolytic manganese dioxide is that manganous sulfate and the direct electrolysis of sulfuric acid make.
Second technical problem to be solved by this invention provides a kind of preparation method of lithium salts hydridization electrolytic manganese dioxide, be specially: contain lithium mineral compound and γ type electrolytic manganese dioxide with Li: Mn=1: 11.0～12.0 mixed in molar ratio is even, in 360～380 ℃ of calcining 6～10h, naturally cool to room temperature and make.
The described lithium mineral compound that contains is at least a in Quilonum Retard, lithium fluoride, the lithium hydroxide.
The 3rd technical problem to be solved by this invention provides that a kind of making method is simple, chemical property lithium salts hydridization electrolytic manganese dioxide battery plate preferably, and it is to be that activeconstituents adds the conventional auxiliary material of electrode slice and makes with above-mentioned lithium salts hydridization electrolytic manganese dioxide.
The 4th technical problem to be solved by this invention provides the making method of above-mentioned lithium salts hydridization electrolytic manganese dioxide battery plate, may further comprise the steps:
The preparation of a, active lithium salts hydridization electrolytic manganese dioxide:
Contain lithium mineral compound and γ type electrolytic manganese dioxide with Li: Mn=1: in 360～380 ℃ of calcinings 6～10 hours, realize phase inversion, dewater behind 11.0～12.0 the mol ratio mixing, naturally cool to room temperature and obtain lithium salts hydridization electrolytic manganese dioxide.
The preparation of b, lithium/manganese dioxide battery pole piece:
Add conductive agent, thinner, emulsifying agent and tackiness agent in the lithium salts hydridization electrolytic manganese dioxide and stir, tumbling becomes to have certain flexible paste; The drying that dewaters becomes dehydration cream piece; Put into b propanol solution and be dipped to state of saturation, become paste with the tumbler tumbling; By extruding type (or rotary) tablets press paste is made particle; By roller press is drawn in the net the roll extrusion of lithium salts hydridization electrolytic manganese dioxide composite grain or stainless steel draws in the net at metallic aluminium, make lithium/manganese dioxide battery pole piece.
The described lithium mineral compound of step a is at least a in Quilonum Retard, lithium fluoride, the lithium hydroxide.
The described conductive agent of step b is at least a in acetylene black, carbon black, the graphite; Thinner is at least a in deionized water, the ethanol; Emulsifying agent is TX-10; Tackiness agent is a polytetrafluoroethyldispersion dispersion.
The 5th technical problem to be solved by this invention provides the application of a kind of lithium salts hydridization electrolytic manganese dioxide battery plate in lithium/manganese dioxide battery.
The present invention has realized the lithium salts hydridization of electrolytic manganese dioxide by the method for " mixing-pyroprocessing ".Contain the lithium mineral compound and add electrolytic manganese dioxide, pass through high-temperature heat treatment, not only remove electrolytic manganese dioxide and contained planar water and the partial crystallization water that contains in the lithium mineral compound, and make the electrolytic manganese dioxide that is mainly the γ type change the electrolytic manganese dioxide of γ and β mixed type into, also realized the manufacturing processed of lithium salts hydridization electrolytic manganese dioxide simultaneously.
Technological process of the present invention is not carried out complicated acid, the liquid " chemical treatment " of alkaloid substance, does not carry out complicated material " mechanical ball milling " simultaneously yet, and only is a kind of " mixing " that simply contains lithium mineral compound and electrolytic manganese dioxide.Its main purpose is both to keep as Mn in the electrolytic manganese dioxide
4+Under the constant prerequisite of positively charged ion total amount, " insertion " lithium ion in the lattice of electrolytic manganese dioxide.This lithium ion is mainly realized " freely inserting " in mixing process, thereby has avoided may causing manganese (Mn in the electrolytic manganese dioxide in the sort of " chemical treatment " and " mechanical ball milling " treating processes
4+) lattice of ionic reduction and electrolytic manganese dioxide makes a variation, keep and improved as lithium/due chemical property of manganese dioxide battery cathode active material.
The battery plate that adopts lithium salts hydridization electrolytic manganese dioxide to make, can significantly improve the low temperature performance of lithium/manganese dioxide battery, the normal temperature loading capacity that is higher than without the lithium/manganese dioxide battery of lithium salts hydridization is not only arranged, and good performance performance is arranged under high-multiplying power discharge, low temperature discharge operating mode.
Embodiment
The invention will be further elaborated below in conjunction with embodiment.Embodiment only is used to illustrate the present invention, rather than limits the present invention by any way.
One, the preparation of lithium salts hydridization electrolytic manganese dioxide
Contain lithium mineral compound and electrolytic manganese dioxide with Li: Mn=1: put into hotblast stove behind 11.0～12.0 the mol ratio mixing in 360～380 ℃ of calcinings 6～10 hours, realize phase inversion, dewater, naturally cool to room temperature and obtain lithium salts hydridization electrolytic manganese dioxide.
The described lithium mineral compound that contains is at least a in Quilonum Retard, lithium fluoride, the lithium hydroxide.
Two, the preparation of lithium/manganese dioxide battery pole piece
Add conductive agent, thinner, emulsifying agent and tackiness agent in the lithium salts hydridization electrolytic manganese dioxide and stir, tumbling becomes to have certain flexible paste; The drying that dewaters becomes dehydration cream piece; Put into b propanol solution and be dipped to state of saturation; Become paste with the tumbler tumbling; By extruding type (or rotary) tablets press paste is made particle; By roller press is drawn in the net the roll extrusion of lithium salts hydridization electrolytic manganese dioxide composite grain or stainless steel draws in the net to make lithium/manganese dioxide battery pole piece at metallic aluminium.
Described conductive agent is at least a in acetylene black, carbon black, the graphite; Thinner is at least a in deionized water, the ethanol; Emulsifying agent is TX-10; Tackiness agent is a polytetrafluoroethyldispersion dispersion.
Three, the preparation of lithium/manganese dioxide battery
Lithium/manganese dioxide battery pole piece will be through drying, cut bar, soldering polar ear, drying, roll, adopt method for winding, be wound into the cylinder core body in the lump with anode strip, barrier film, insert in the nickel plating box hat, welding cathode and anode lug, soldering and sealing (or argon arc welding or Laser Welding) housing, perfusion electrolytic solution, the soldering and sealing liquid filling hole makes lithium/manganese dioxide battery.
Described anode strip is selected metallic lithium foil for use, and its lithium content is 99.9%.In order to improve the lithium anode discharge performance, make full use of the lithium anode active substance, reduce inside battery resistance, need on the lithium paper tinsel, inlay nickel wire (or nickel foil or nickel screen or stainless steel foil) as collector bar, lug generally adopts nickel (or stainless steel) paper tinsel band, and realizes that with the lithium paper tinsel reliable cold welding connects.
Employed barrier film is selected apertured polymeric film between anode strip and lithium/manganese dioxide cathodes sheet, as polypropylene (PP), polyethylene (PE), PP/PE composite membrane, this apertured polymeric film has higher chemical stability in lithium/manganese dioxide battery system, both prevented that negative electrode, anode, ionogen, barrier film from producing corrosion and influence mutually, electrolyte ion can also successfully be passed through by micropore simultaneously.
The electrolytic solution of battery is made up of non-aqueous eletrolyte and ionogen, non-aqueous eletrolyte is selected the organic solvent that the high-and low-temperature resistance performance is good, specific conductivity is higher usually, and adopt polynary mixed system, as propylene carbonate (PC), glycol dimethyl ether (DME), dioxolane (DOL), gamma-butyrolactone (at least a in γ-BL), the tetrahydrofuran (THF) (THF).Ionogen is selected more stable lithium salts usually, as lithium perchlorate (LiClO
4), lithium hexafluoro phosphate (LiPF
6), hexafluoroarsenate lithium (LiAsF
6), LiBF4 (LiAsF
4), trifluoromethyl sulfonic acid lithium (LiCF
3SO
3) etc.The electrolytic solution of battery is preferably lithium perchlorate (LiClO
4) be dissolved in the mixed solution of PC, DME, γ-BL, concentration 1.0-1.2M/L, PC: DME: γ-BL was by weight 4: 4: 2 ratio preparation.
The employed starting material of following examples:
Electrolytic manganese dioxide (EMD) is that Xiang Tan electrification Science and Technology Co., Ltd. produces Manganse Dioxide content 92.64%, H
2O content 1.22%, pH value are 6.52.
Lithium Hydroxide Monohydrate (LiOHH
2O), Quilonum Retard (Li
2CO
3), lithium fluoride (LiF) is that Dianfeng Lithium Industry Co., Ltd. produces, wherein lithium hydroxide (LiOH) content 56.7%, Quilonum Retard (Li
2CO
3) content is 0.21%, lithium fluoride (LiF) content is 99.9%;
Lithium anode is that center is built the production of center limited fuel, and wherein Li content is 99.9%, thickness: 0.17mm;
The polypropylene micro-pore septum is produced model: 2325 for U.S. Celgard.
Embodiment 1
The preparation of the first step lithium salts hydridization electrolytic manganese dioxide
Take by weighing the 11000g electrolytic manganese dioxide, the 458g Lithium Hydroxide Monohydrate is poured in 40L " V " the type mixer, opens mixer with 40 rev/mins of batch mixings of velocity of rotation 10 minutes.Material is poured in the stainless steel pallet, put into hotblast stove, naturally cool to room temperature and promptly get lithium salts hydridization electrolytic manganese dioxide in 370 ℃ of calcinings 8 hours.
The preparation of the second step lithium salts hydridization electrolytic manganese dioxide battery plate
In lithium salts hydridization electrolytic manganese dioxide 11000g, add acetylene black 1300g, polytetrafluoroethyldispersion dispersion (60%) 1200g, emulsifying agent (TX-10) 180g and deionized water 4700g successively, stir, be mixed into paste; Paste is put into baking oven (120 ± 10 ℃), and drying dewaters; Put into b propanol solution after the cooling and be dipped to state of saturation; Pass through the rotating-expressing type tablets press after the dehydration cream piece usefulness tumbler tumbling with state of saturation, make irregular particle, particle diameter is less than 6mm; Use is drawn in the net roll extrusion together to roller press with particulate matter and aluminium, makes pole piece; At last with pole piece oven dry, cut bar, soldering polar ear, oven dry again, roll extrusion promptly gets lithium salts hydridization electrolytic manganese dioxide battery plate again.
The preparation of the 3rd step lithium/manganese dioxide battery
Lithium anode, lithium salts hydridization electrolytic manganese dioxide cell cathode, polypropylene micro-pore septum are wound into the battery core body in the lump, insert in the nickel plating box hat, the welded cathode lug, install additional metallic glass envelope, argon arc girth welding box hat with the metallic glass envelope, pour into electrolytic solution, soldering and sealing liquid filling hole, produce the sample battery.
The 4th step battery performance test
8 on random sampling product battery is made electric performance test, carries out the test of open circuit voltage and load voltage at first at ambient temperature, does normal temperature and low temperature volume test then respectively, wherein uses the 500mA constant-current discharge for 4 under normal temperature (23 ℃); Use the 500mA constant-current discharge for other 4 under low temperature (20 ℃), discharge the results are shown in Table 1.
Table 1 battery sample normal temperature, low temperature constant-current discharge result
Embodiment 2
The preparation of the first step lithium salts hydridization electrolytic manganese dioxide
Take by weighing the 11000g electrolytic manganese dioxide, the 385g Quilonum Retard is poured in 40L " V " the type mixer, opens mixer with 40 rev/mins of batch mixings of velocity of rotation 10 minutes.Material is poured in the stainless steel pallet, put into hotblast stove, naturally cool to room temperature and promptly get lithium salts hydridization electrolytic manganese dioxide in 370 ℃ of calcinings 8 hours.
The preparation of the second step lithium salts hydridization electrolytic manganese dioxide battery plate
The kind of additive, consumption, manufacture craft are identical with embodiment 1.
The preparation of the 3rd step lithium/manganese dioxide battery
Battery winding, ionogen proportioning, electrolytic solution perfusion, cell making process are identical with embodiment 1.
The 4th step battery performance test
8 on random sampling product battery is made electric performance test, and testing method is identical with embodiment 1, and discharge the results are shown in Table 2.
Table 2 battery sample normal temperature, low temperature constant-current discharge result
Embodiment 3
The preparation of the first step lithium salts hydridization electrolytic manganese dioxide
Take by weighing 11000g electrolytic manganese dioxide, 275g Quilonum Retard, 110g lithium fluoride and pour in 40L " V " the type mixer, open mixer with 40 rev/mins of batch mixings of velocity of rotation 10 minutes.Material is poured in the stainless steel pallet, put into hotblast stove, naturally cool to room temperature and promptly get lithium salts hydridization electrolytic manganese dioxide in 370 ℃ of calcinings 8 hours.
The preparation of second step lithium salts hydridization electrolysis titanium dioxide battery plate
The kind of additive, consumption, manufacture craft are identical with embodiment 1.
The preparation of the 3rd step lithium/manganese dioxide battery
Battery winding, ionogen proportioning, electrolytic solution perfusion, cell making process are identical with embodiment 1.
The 4th step battery performance test
8 on random sampling product battery is made electric performance test, and testing method is identical with embodiment 1, and discharge the results are shown in Table 3.
Table 3 battery sample normal temperature, low temperature constant-current discharge result
Embodiment 4 (contrast sample)
The preparation of the first step electrolytic manganese dioxide
Take by weighing the 11000g electrolytic manganese dioxide and pour in the stainless steel pallet, put into hotblast stove, naturally cool to room temperature in 370 ℃ of calcinings 8 hours.
By above operation, remove planar water and the partial crystallization water removed in the material, make electrolytic manganese dioxide change γ and β mixed type into, as the contrast sample of non-lithium salts hydridization electrolytic manganese dioxide by being mainly the γ type.
The preparation of the second one-step electrolysis titanium dioxide battery plate
The kind of additive, consumption, manufacture craft are identical with embodiment 1.
The preparation of the 3rd step lithium/manganese dioxide battery
Battery winding, ionogen proportioning, electrolytic solution perfusion, cell making process are identical with embodiment 1.
The 4th step battery performance test
8 on random sampling product battery is made electric performance test, and testing method is identical with embodiment 1, and discharge the results are shown in Table 4.
Table 4 battery sample normal temperature, low temperature constant-current discharge result
Lithium/the manganese dioxide battery that adopts lithium salts hydridization electrolytic manganese dioxide to make, the load voltage at its 5 Ω/5s end is minimum to be 2.81V, is up to 2.82V; Low temperature-20 ℃, the 500mA discharge is minimum to be 348mAh, is up to 438mAh.And lithium/manganese dioxide battery of making without lithium salts hydridization electrolytic manganese dioxide, the load voltage at its 5 Ω/5s end only is 2.70V; Low temperature-20 ℃, the 500mAh discharge only is 140mAh.Lithium salts hydridization electrolytic manganese dioxide of the present invention can significantly improve the low temperature performance of lithium/manganese dioxide battery, the normal temperature loading capacity that is higher than without the lithium/manganese dioxide battery of lithium salts hydridization is not only arranged, and good performance performance is arranged under high-multiplying power discharge, low temperature discharge operating mode.
Claims (8)
1. lithium salts hydridization electrolytic manganese dioxide, it is characterized in that: it is by containing lithium mineral compound and γ type electrolytic manganese dioxide with Li: Mn=1: 11.0～12.0 mixed in molar ratio is even, in 360～380 ℃ of calcinings 6～10 hours, naturally cool to room temperature and make.
2. lithium salts hydridization electrolytic manganese dioxide according to claim 1 is characterized in that: the described lithium mineral compound that contains is at least a in Quilonum Retard, lithium fluoride, the lithium hydroxide.
3. the preparation method of the described lithium salts hydridization of claim 1 electrolytic manganese dioxide, it is characterized in that: contain lithium mineral compound and γ type electrolytic manganese dioxide with Li: Mn=1: 11.0～12.0 mixed in molar ratio evenly after, in 360～380 ℃ of calcinings 6～10 hours, naturally cool to room temperature and make.
4. lithium salts hydridization electrolytic manganese dioxide battery plate is characterized in that: it is to be that activeconstituents adds the conventional auxiliary material of electrode slice and makes with the described lithium salts hydridization of claim 1 electrolytic manganese dioxide.
5. the preparation method of the described lithium salts hydridization of claim 4 electrolytic manganese dioxide battery plate, it is characterized in that: add the tumbling that stirs of conductive agent, thinner, emulsifying agent and tackiness agent in the lithium salts hydridization electrolytic manganese dioxide and become to have certain flexible paste, the drying that dewaters becomes dehydration cream piece, put into b propanol solution and be dipped to state of saturation, become paste with the tumbler tumbling, paste is made particle by extruding type (or rotary) tablets press; By roller press is drawn in the net the roll extrusion of lithium salts hydridization electrolytic manganese dioxide composite grain or stainless steel draws in the net to make at metallic aluminium.
6. the preparation method of salt hydridization electrolytic manganese dioxide battery plate according to claim 4 is characterized in that: described conductive agent is at least a in acetylene black, carbon black, the graphite; Thinner is at least a in deionized water, the ethanol; Emulsifying agent is TX-10; Tackiness agent is a polytetrafluoroethyldispersion dispersion.
7. the application of the described lithium salts hydridization of claim 1 electrolytic manganese dioxide in lithium cell.
8. lithium/manganese dioxide battery is characterized in that: it is to reel or the lamination moulding with the described lithium salts hydridization of claim 4 electrolytic manganese dioxide battery plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200810301843XA CN101279768A (en) | 2008-05-30 | 2008-05-30 | Hybridization method of lithium salt and electrolytic manganese dioxide, application thereof to lithium battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200810301843XA CN101279768A (en) | 2008-05-30 | 2008-05-30 | Hybridization method of lithium salt and electrolytic manganese dioxide, application thereof to lithium battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102361070A (en) * | 2011-11-08 | 2012-02-22 | 天津市泰豪锂电池有限公司 | Process for preparing positive pole of lithium battery |
| CN103814468A (en) * | 2013-09-27 | 2014-05-21 | 惠州亿纬锂能股份有限公司 | Electrolyte for lithium battery and lithium battery using the electrolyte |
| CN112216815A (en) * | 2019-07-11 | 2021-01-12 | 深圳市比亚迪锂电池有限公司 | Lithium manganese battery positive electrode and lithium manganese battery |
-
2008
- 2008-05-30 CN CNA200810301843XA patent/CN101279768A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102361070A (en) * | 2011-11-08 | 2012-02-22 | 天津市泰豪锂电池有限公司 | Process for preparing positive pole of lithium battery |
| CN103814468A (en) * | 2013-09-27 | 2014-05-21 | 惠州亿纬锂能股份有限公司 | Electrolyte for lithium battery and lithium battery using the electrolyte |
| CN103814468B (en) * | 2013-09-27 | 2018-07-06 | 惠州亿纬锂能股份有限公司 | A kind of electrolyte for lithium cells and the lithium battery using the electrolyte |
| CN112216815A (en) * | 2019-07-11 | 2021-01-12 | 深圳市比亚迪锂电池有限公司 | Lithium manganese battery positive electrode and lithium manganese battery |
| CN112216815B (en) * | 2019-07-11 | 2021-12-07 | 深圳市比亚迪锂电池有限公司 | Lithium manganese battery positive electrode and lithium manganese battery |
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Application publication date: 20081008 |