CN1074175C - Non-aqueous electrolyte lithium manganese battery - Google Patents
Non-aqueous electrolyte lithium manganese battery Download PDFInfo
- Publication number
- CN1074175C CN1074175C CN92113611A CN92113611A CN1074175C CN 1074175 C CN1074175 C CN 1074175C CN 92113611 A CN92113611 A CN 92113611A CN 92113611 A CN92113611 A CN 92113611A CN 1074175 C CN1074175 C CN 1074175C
- Authority
- CN
- China
- Prior art keywords
- negative electrode
- liclo
- dme
- dol
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000011255 nonaqueous electrolyte Substances 0.000 title abstract 3
- 239000003792 electrolyte Substances 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 11
- 239000006230 acetylene black Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 4
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000001186 cumulative effect Effects 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000001125 extrusion Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 7
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 abstract 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 abstract 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- PZZOEXPDTYIBPI-UHFFFAOYSA-N 2-[[2-(4-hydroxyphenyl)ethylamino]methyl]-3,4-dihydro-2H-naphthalen-1-one Chemical compound C1=CC(O)=CC=C1CCNCC1C(=O)C2=CC=CC=C2CC1 PZZOEXPDTYIBPI-UHFFFAOYSA-N 0.000 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229940095991 ferrous disulfide Drugs 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Classifications
-
- 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
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a non-aqueous electrolyte lithium manganese battery, in particular to a cathode composition and an electrolyte of the batteryAnd (4) preparing the system. The cathode is made of MnO2、V2O5、Me(OH)2Acetylene black and polytetrafluoroethylene, wherein Me represents Mg, Ca, Sr and Ba; the electrolytic liquid is one of the following three types:
a.LiClO4+PC/DME+1，3-DOL；
b.LiClO4+PC/4M-1，3-DOL+1，3-DOL；
c.LiClO4+PC/DME+THF+C6H5CH5；
one of the three electrolyte systems and the cathode are added with high-purity lithium to form the non-aqueous electrolyte lithium manganese battery. The battery has good high-voltage and low-temperature performances, the normal-temperature short-circuit current can reach more than 600mA, the low-temperature applicable temperature is up to-40 ℃, and the battery can be used for manufacturing batteries of models such as CR2025, CR11108, CR17335 and the like.
Description
The present invention relates to a kind of lithium manganese series cell, belong to technical field of chemical power, particularly the negative electrode composition and the electrolyte system of this series battery.
Set forth 2 points in the United States Patent (USP) 4229691 disclosed " ternary mixture solvent ", the one, the ternary mixture solvent consist of PC, DME and 1,3-DOL, the proportioning of every kind of component is 20～60% (volume ratios); The 2nd, the cell cathode of this electrolyte (do not put forward electrolytical concentration, also do not put forward the Applicable temperature scope) can be cupric oxide or ferrous disulfide; In other words, the battery that provides of this patent is Li/CuO or Li/FeS
2Battery system, the nominal voltage of these two kinds of batteries is 1.5V.
Reported among the special permission communique (B-2) that Japan delivers, the flat 1-27550 and in negative electrode, added Me (OH)
2Purpose be the expansion issues that solves battery, the electrolyte that this battery adopts is LiClO
4+ PC/DME, conclusion is to add Me (OH) in negative electrode
2Back (wherein Me represents Mg, Ca, Sr, Ba), (200～400 ℃ of electrical properties of handling to obtain down are better than what handle at normal temperatures at high temperature again.
Another piece Progress In Batteries ﹠amp; Solar Cells.Vol.8, in (1989), the single-minded report adds V in the negative electrode
2O
5The height that can improve battery is put performance, and its used electrolyte system also is LiClO
4+ PC/DME, cathode active material are CMD (chemical MnO
2), this battery does not possess good cryogenic property yet.
At present, in existing technology, (comprise product both domestic and external), because negative electrode is by MnO
2+ acetylene black+polytetrafluoroethylene is formed, MnO
2Account for about 85% of total amount, acetylene black accounts for about 10%, and polytetrafluoroethylene accounts for about 5%, MnO
2Heat treatment temperature be 350～450 ℃, in order to dewater, general normal employing is higher than 400 ℃ temperature.With this understanding, can produce two negative consequences, the one, some MnO
2Changed into inactive Mn
2O
3(temperature is high more, MnO
2Growing amount big more, this conversion is particularly evident under the situation of anoxic), except making active MnO
2Measure outside corresponding minimizing, the discharge capacity reduction, also increased the internal resistance of battery, the voltage of battery is descended; The 2nd, under this temperature, β phase MnO
2Increase (to 450 ℃ time almost be the β phase entirely), β phase MnO
2Not only poor activity, and specific area greatly reduces, and so also just correspondingly having reduced height puts performance and discharge capacity.In fact, such negative electrode also exists the 3rd unfavorable factor, i.e. MnO
2Though through heat treatment, still chemisorbed hydroxy functional group on its surface, hydroxy functional group can be at MnO
2Catalysis turn into under discharge proton (H
+) come, the generation of proton causes electric liquid to be acid, PC is decomposed produce gas, and the generation of gas causes the swelling of battery and internal resistance to increase again, finally causes battery electrical property to degenerate.In addition, because polytetrafluoroethylene proportion in negative electrode is bigger, this minimizing that not only has influence on active matter quality reduces discharge capacity, and because polytetrafluoroethylene is an electrical insulator, it measures increase, will increase the internal resistance of battery undoubtedly, reduces the electric conductivity of battery.
The electrochemical system of existing lithium-manganese cell is Li/LiClO
4+ PC+DME/MnO
2(CMD), it is bad that this electrochemical system has been acknowledged as its cryogenic property, and height to put performance also poor, can not satisfy growing to height put, the requirement of cryogenic property.The bad reason of electrical property shows electrolyte system 1Mol-LiClO respectively
4On+PC/DME (volume ratio 1: 1) and the two-part composition of negative electrode.The electrolytic salinity of this electrolyte less (being generally 1M), the flowability under the low temperature is poor, and general minimum Applicable temperature can only arrive-20 ℃, and normal temperature, high-temperature shelf property are poor; Negative electrode is perfect inadequately on forming, and internal resistance is bigger, and therefore, poorly conductive does not promptly possess height and puts performance.
A present international and domestic lithium manganese (Li/MnO
2) trend of battery development be to height put, the cryogenic property direction develops, and existing lithium-manganese cell does not all reach this requirement.Purpose of the present invention in order to overcome the deficiencies in the prior art, is formed with the discharge rate of raising battery and the shelf characteric of discharge capacity and battery by selecting rational negative electrode exactly; Aspect electrolyte system, adopt low melting point more, can dissolve the solvent of electrolytic salt in a large number, with flowability and the conducting power that improves electric liquid, adopt the solvent that has methyl rational in infrastructure simultaneously, to guarantee chemistry and the electrochemical stability of whole electrochemical system in battery, so just can make the performance of nonaqueous electrolytic solution lithium-manganese cell reach comparatively perfect degree, make it not only have a height and put performance but also tool cryogenic property, the normal temperature short circuit current can reach more than the 600mA, and the low temperature Applicable temperature is to-40 ℃.
In order to address the above problem, the solution that the present invention adopts is in the nonaqueous electrolytic solution lithium-manganese cell, to be emphatically the improvement that the composition and the manufacture method of electrolyte system and negative electrode are done.
About electrolyte system, the present invention proposes three kinds altogether:
A.LiClO
4+ PC/DME+1,3-DOL, wherein LiClO
4Concentration be 0.8～1.5M; The ratio of PC: DME is 1～1.5; 1,3-DOL shared percent by volume in three kinds of solvents is 20～80%; The characteristics of this electrolyte system are to have good low temperature flow and the relatively large dissolving electrolytic salt (LiClO of energy
4), this system that Here it is has excellent cryogenic property and high reason of putting performance;
B.LiClO
4+ PC/4M-1,3-DOL+1,3-DOL, the content of each composition and a's is identical in this system, just change DME into 4M-1,3-DOL, this individual system is also more quite a lot of than a, the advantage that it possesses in a, the height that also possesses better chemistry and electrochemical stability and Geng Gao is put performance (exceeding about 10% than a);
C.LiClO
4+ PC/DME+THF+C
6H
5CH
3, LiClO in this system
4Molar concentration be 1M; The volume ratio of PC: DME: THF was approximately equal to 1: 1: 1; C
6H
5CH
3Account for 3～7% of cumulative volume; The normal temperature performance and the prior art of this individual system are suitable, but cryogenic property is but good than prior art, and its low temperature (40 ℃) performance is better than system a.
Form and manufacture method about negative electrode:
Negative electrode is by MnO
2(electrolytic manganese powder), V
2O
5, Me (OH)
2(Me represents Mg, Ca, Sr, Ba), acetylene black, polytetrafluoroethylene are formed.MnO wherein
2Account for 85～87% of negative electrode total weight, V
2O
5Account for 1.65～1.81% of negative electrode total weight, Me (OH)
2Account for 0.57～1.15% of negative electrode total weight, acetylene black accounts for 9～11% of negative electrode total weight, and polytetrafluoroethylene accounts for 1.8～2.4% of negative electrode total weight.
Manufacture method is MnO
2Be 85～87%, add 1.65～1.81% V again
2O
5, at 375～400 ℃ of following heat treatment 5h, under air-tight state, be cooled to room temperature then, add Me (OH) again
20.57～1.15%, mixing is placed more than the 24h, adds acetylene black 9～11% and polytetrafluoroethylene 1.8～2.4% at last, mixing, and press molding is dried in baking oven, is negative electrode.
Negative electrode adopts above-mentioned prescription and processing method, has improved the discharge capacity and the discharge rate of battery, and has improved shelf characteric.
One of this negative electrode and above-mentioned three kinds of electric liquid system (selecting as required) are added high purity lithium and are done anode, just can form nonaqueous electrolytic solution lithium-manganese cell of the present invention.
The composition of three electrolyte systems of the present invention is all reasonable than prior art.In first kind of electrolyte system, owing to added 1,3-DOL makes the performance of whole electrolyte system that great change take place, and promptly the low temperature flow of electrolyte is better, electrolytic salt LiClO
4The molar concentration scope increase, improved the conductive performance of ion greatly, and, the chemical stability of battery and shelf characteric also had some improvement because the ratio of DME in whole electric liquid diminishes; The low temperature scope of application of battery enlarges, and reaches about-40 ℃, has realized the high purpose that performance and cryogenic property are taken into account simultaneously of putting.For second electric liquid system of the present invention, owing to used the improved 4M-1 of chemical constitution, 3-DME replaces DME, the conducting power of electrolyte is improved, and improved the chemistry and the electrochemical stability of whole electrochemical system.This electric liquid system not only is better than prior art, and better than the performance of first kind of electrolyte system of the present invention, and its normal temperature height is put performance than will the exceeding about 10% of first kind of electrolyte system, and cryogenic property is approaching substantially.About the third electrolyte system of the present invention, because the fusing point of THF very low (fusing point of THF is-58 ℃, 1, the fusing point of 3-DOL is-95 ℃), therefore, the low temperature flow of this electrolyte is fine, and adds cosolvent C therein
6H
5CH
3, make THF because of harmful deposit that the corrosion lithium anode produces obtains dissolving, the cryogenic property of battery is further improved.
Negative electrode of the present invention aspect is primarily aimed at the deficiency that prior art exists, and has taked some effective measures on negative electrode composition and manufacture method thereof.Generally speaking, the cryogenic property of battery depends primarily on the composition of electrolyte, and the height of battery is put composition and the manufacture method thereof that performance then depends primarily on negative electrode.But the two is not isolated fully, but interactional.In negative electrode, add V
2O
5And Me (OH)
2, its effect is significantly, V
2O
5Both can stop MnO
2Be converted into Mn
2O
3, can stop β phase MnO again
2Generation because its existence has improved Li
+To MnO
2The speed of diffusion in the lattice, this can not only make the discharge capacity of battery improve, and the more important thing is that the height that has improved battery puts performance.Add Me (OH)
2Can neutralize the acid that produces owing to aforementioned factor in the electrolyte, thereby can eliminate the generation of a series of adverse reactions, both hold electrical property, guarantee that again the overall dimension of battery is constant.In addition, because the amount of polyfluortetraethylene of binding element is reduced to 1.8～2.4% by original 5～8% in the negative electrode, also be favourable undoubtedly to reducing the internal resistance of cell, improving electric conductivity, because of polytetrafluoroethylene is an insulator, its amount in negative electrode should be low as much as possible.
Embodiment:
CR2025, the CR11108 that the current series invention is made and three kinds of the widest batteries of present purposes of CR17335 are that example is further set forth effect of the present invention.
Have great number tested data to prove, the present invention is compared with prior art put at the height of battery and all have been obtained breakthrough aspect performance and the cryogenic property.
One. put aspect of performance at height, the normal temperature short-circuit current value of CR2025 battery of the present invention can reach more than the 600mA, and the short-circuit current value of the CR2025 battery of prior art is generally about 200mA; The discharge data that records under the uniform temp condition with the battery of the same type of the battery of negative electrode of the present invention and first kind of electrolyte system a assembling and domestic and international representational producer sees Table 1.
Table 1 the present invention and the comparison of battery of the same type performance both at home and abroad
| Yi Li Changzhou, producer PANASONIC Hong Kong reaches power the present invention |
| The CR2025 battery connect under-40 ℃ continuous time (about 0.93mA) (about 1.87mA) 43 ' .30 " 4h53 ' 38 " the CR2025 battery that is discharged to 2.0V of 3K Ω load 1.5K Ω load-40 ℃, repeatedly measure repeatedly measure repeatedly measure under 350 Ω continuous discharge to the 2.0V fluctuation in time～2 of 1 ' fluctuation 50 " fluctuating 30 " " about left and right sides CR2025 battery load the time of continuous discharge to 2.0V at normal temperature, 600 19.5h 50.5h Ω |
Two. as the CR11108 battery, adopt second kind of electrolyte system b, continuous discharge to 2.5 under normal temperature, 1.4K Ω (being equivalent to 2mA) load, its discharge capacity is 220mAh; And Unite States Standard is that continuous discharge is to 2.0V under 2.7K Ω (the being equivalent to 1mA) load, and discharge capacity only is 160mA.
Three. and for example aspect cryogenic property, the CR17335 battery adopts the third electrolyte system c, and continuous discharge records discharge capacity and reaches more than 70% of normal temperature capacity to 2.0V under-30 ℃, 200 Ω load.
Battery of the present invention the discharge middle and later periods magnitude of voltage correspondingly than the battery height of prior art, this just makes that also discharge capacity of the cell of the present invention is increased, and has improved height and has put performance.
Claims (2)
1. a nonaqueous electrolytic solution lithium-manganese cell is made up of negative electrode, electrolyte system and high purity lithium anode, and it is characterized in that: negative electrode is by MnO
2, V
2O
5, Me (OH)
2, acetylene black and polytetrafluoroethylene form, wherein Me represents Mg, Ca, Sr, Ba; Each composition proportion is in the negative electrode: MnO
2Account for 85～87% of negative electrode total weight, V
2O
5Account for 1.61～1.81% of negative electrode total weight, Me (OH)
2Account for 0.57～1.71% of negative electrode total weight, acetylene black accounts for 9～11% of negative electrode total weight, and polytetrafluoroethylene accounts for 1.8～2.4% of negative electrode total weight;
Electrolyte is one of following three kinds:
A.LiClO
4+ PC/DME+1,3-DOL, wherein LiClO
4Molar concentration be 0.8～1.5M, the ratio of PC/DME is 1～1.5,1,3-DOL shared percent by volume in three kinds of solvents is 20～80%;
B.LiClO
4+ PC/4M-1,3-DOL+1,3-DOL, wherein the content of each composition and percent by volume and a's is identical, just changes DME into 4M-1,3-DOL;
C.LiClO
4+ PC/DME+THF+C
6H
5CH
3, LiClO wherein
4Molar concentration be 1M, the volume ratio of PC: DME: THF is 1: 1: 1, C
6H
5CH
3Account for 3～7% of cumulative volume.
2. the manufacture method of a nonaqueous electrolytic solution Cathode of lithium-manganese cell comprises operations such as heat treatment, cooling, moulding, oven dry, it is characterized in that 85～87% MnO
2With 1.61～1.81% V
2O
5Mix,, under air-tight state, be cooled to room temperature then, add 0.57～1.71% Me (OH) more earlier at 375～400 ℃ of following heat treatment 5h
2And mix, place more than the 24h, add 9～11% acetylene black and 1.8～2.4% polytetrafluoroethylene at last, mix, extrusion forming is dried in baking oven.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92113611A CN1074175C (en) | 1992-11-19 | 1992-11-19 | Non-aqueous electrolyte lithium manganese battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92113611A CN1074175C (en) | 1992-11-19 | 1992-11-19 | Non-aqueous electrolyte lithium manganese battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1087449A CN1087449A (en) | 1994-06-01 |
| CN1074175C true CN1074175C (en) | 2001-10-31 |
Family
ID=4946512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92113611A Expired - Fee Related CN1074175C (en) | 1992-11-19 | 1992-11-19 | Non-aqueous electrolyte lithium manganese battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1074175C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344017C (en) * | 2005-05-25 | 2007-10-17 | 厦门大学 | Method for preparing MnO2/silver composite cathode of Li-Mn cell |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063582C (en) * | 1996-11-26 | 2001-03-21 | 厦门大学 | Method for manufacturing positive electrode of manganese series battery |
| KR101539780B1 (en) * | 2006-08-22 | 2015-07-27 | 미쓰비시 가가꾸 가부시키가이샤 | 2 2 2 2 lithium difluorophosphate electrolytic solution containing lithium difluorophosphate process for producing lithium difluorophosphate process for producing nonaqueous electrolytic solution nonaqueous electrolytic solution and nonaqueous-electrolytic-solution secondary cell employing the same |
| EP3258521B1 (en) * | 2016-06-14 | 2020-11-04 | VARTA Microbattery GmbH | Lithium primary cell with dme-free electrolytes |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4585715A (en) * | 1984-06-29 | 1986-04-29 | Union Carbide Corporation | Metal cathode collector having a protective surface layer of a metal oxide |
| US4737424A (en) * | 1985-11-01 | 1988-04-12 | Nippon Telegraph & Telephone Corporation | Secondary lithium battery |
-
1992
- 1992-11-19 CN CN92113611A patent/CN1074175C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4585715A (en) * | 1984-06-29 | 1986-04-29 | Union Carbide Corporation | Metal cathode collector having a protective surface layer of a metal oxide |
| US4737424A (en) * | 1985-11-01 | 1988-04-12 | Nippon Telegraph & Telephone Corporation | Secondary lithium battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344017C (en) * | 2005-05-25 | 2007-10-17 | 厦门大学 | Method for preparing MnO2/silver composite cathode of Li-Mn cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1087449A (en) | 1994-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110350164B (en) | Multiphase composite high-nickel ternary positive electrode material and preparation method thereof | |
| CN113991178B (en) | Nonaqueous electrolyte for lithium ion battery and application thereof | |
| CN109119632A (en) | Positive electrode slurry, positive plate and lithium ion battery | |
| CN113611839A (en) | Novel mixed system lithium-rich manganese-based positive plate and preparation method thereof, and lithium ion battery | |
| CN109411706B (en) | Modified working electrode and preparation method thereof | |
| CN114284476A (en) | Preparation method of carbon composite sodium-ion battery positive electrode material | |
| CN1074175C (en) | Non-aqueous electrolyte lithium manganese battery | |
| CN111653769A (en) | Lithium ion battery with wide temperature range | |
| CN115966769A (en) | Local high-concentration lithium metal battery electrolyte and preparation method and application thereof | |
| KR20240046809A (en) | Low-temperature lithium-ion battery electrolyte and its manufacturing method and lithium-ion battery | |
| WO2024066088A1 (en) | Secondary battery and electrical device | |
| CN113206292B (en) | Polymer-based composite solid electrolyte and preparation method and application thereof | |
| CN115275166A (en) | Long-life graphite composite material and preparation method thereof | |
| CN114597077A (en) | Application of pre-lithiated carbon negative electrode material in sodium ion capacitor and potassium ion capacitor | |
| CN114204118A (en) | PVDF (polyvinylidene fluoride) -based composite solid electrolyte and preparation method thereof | |
| CN112310478A (en) | Electrolyte and electrochemical device thereof | |
| CN115571908B (en) | Lithium titanate electrode material and application thereof in composite battery and standby power supply | |
| CN114899484B (en) | Nonaqueous electrolyte and lithium ion battery thereof | |
| CN113793936B (en) | Composite binder for solid lithium battery and preparation method and application thereof | |
| CN113224295B (en) | Preparation method and application of asphalt-based nano carbon sheet | |
| WO2024108417A1 (en) | Aqueous dual-ion battery and preparation method therefor | |
| CN110459735B (en) | Cathode material, preparation method thereof, battery cathode and lithium ion battery | |
| CN118198502A (en) | Lithium metal battery electrolyte and lithium metal battery | |
| CN116093419A (en) | Organic-inorganic composite solid electrolyte, preparation method thereof and solid lithium battery | |
| CN116315094A (en) | Sodium ion battery electrolyte and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| OR01 | Other related matters | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |