CN108493444A - A kind of anode of li-Mn button cell and preparation method thereof - Google Patents
A kind of anode of li-Mn button cell and preparation method thereof Download PDFInfo
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
The invention discloses a kind of anodes of li-Mn button cell and preparation method thereof, including positive active material manganese dioxide, graphite, acetylene black, polytetrafluoroethylene (PTFE), wherein manganese dioxide passes through high-temperature heat treatment, by α MnO2 and γ the MnO2 crystal structure transitions contained inside it at γ MnO2 and β MnO2 mixing crystalline structures, the ratio that β MnO2 crystal forms account for mixing crystal form is set to reach between 60 80%, and the content of manganese dioxide internal crystallization water also accordingly reduces, manganese dioxide activity after being heat-treated in this way greatly enhances, substantially increase the capacity and large current discharging capability of battery.
Description
Technical field
The present invention relates to battery material technology of preparing, anode and its preparation of a kind of li-Mn button cell are particularly related to
Method belongs to electrochemical field.
Background technology
Lithium-manganese dioxide button cell is a kind of energy-storage battery to grow up the 1970s, due to its have than
Energy is high, and long lifespan, self discharge is small, cost-effective, it is pollution-free the advantages that, show big advantage in the application,
It is widely used in calculator, electronic watch, automobile remote-control key, communication device etc..With the development of electronic information technology, to battery
Higher requirements are also raised for various aspects performance, and especially the requirement to the discharge capacity of battery and power density is increasingly
It is high.Existing lithium battery is disadvantageous in that battery capacity and High-current output performance are relatively low, has seriously affected answering extensively for it
With.
Therefore, there is an urgent need for a kind of new technologies of design to improve its problem by the present inventor.
Invention content
The present invention is intended to provide a kind of anode of li-Mn button cell and preparation method thereof, can improve lithium battery capacity
And large current discharging capability.
In order to solve the above technical problems, the technical scheme is that：
A kind of anode of li-Mn button cell, including positive active material manganese dioxide, graphite, acetylene black, polytetrafluoroethyl-ne
Alkene, wherein manganese dioxide pass through high-temperature heat treatment, by the α-MnO2 contained inside it and γ-MnO2 crystal structure transitions at γ-
MnO2 and β-MnO2 mix crystalline structure, and β-MnO2 crystal forms account for the ratio of mixing crystal form and reach between 60-80%.
Preferably, manganese dioxide is 80-95 parts by weight in the positive active material, and graphite is 1-10 parts by weight, acetylene
Black is 1-5 parts by weight, and polytetrafluoroethylene (PTFE) is 1-5 parts by weight.
Preferably, manganese dioxide is 92 parts by weight in the positive active material, and graphite is 4 parts by weight, and acetylene black is 2 weights
Part is measured, polytetrafluoroethylene (PTFE) is 2 parts by weight.
A kind of anode preparation method of li-Mn button cell, includes the following steps：
S1:Electrolytic manganese dioxide is sintered 10-20h in sintering furnace under the conditions of 350-440 DEG C；
S2:Sintered manganese dioxide and graphite, acetylene black, polytetrafluoroethylene material are sufficiently mixed；
S3:Being prepared by techniques such as dry mixing, wet-mixing, tabletting, granulation, film-making, dryings becomes positive plate.
Preferably, electrolytic manganese dioxide is sintered 12h in sintering furnace under the conditions of 375 DEG C in the step S1.
Preferably, electrolytic manganese dioxide is sintered 16h in sintering furnace under the conditions of 405 DEG C in the step S1.
Preferably, electrolytic manganese dioxide is sintered 20h in sintering furnace under the conditions of 440 DEG C in the step S1.
Preferably, electrolytic manganese dioxide is sintered 10h in sintering furnace under the conditions of 350 DEG C in the step S1.
Preferably, in the step S2 by manganese dioxide according to 80-95 parts by weight, graphite 1-10 parts by weight, acetylene black 1-5
Parts by weight, polytetrafluoroethylene (PTFE) 1-5 parts by weight are sufficiently mixed.
Preferably, in the step S2 by manganese dioxide according to 92 parts by weight, 4 parts by weight of graphite, 2 parts by weight of acetylene black,
2 parts by weight of polytetrafluoroethylene (PTFE) are sufficiently mixed.
Using above-mentioned technical proposal, the present invention includes at least following advantageous effect：
The anode and preparation method thereof of li-Mn button cell of the present invention, manganese dioxide crystalline structure change,
It is transformed into γ-MnO2 and β-MnO2 mixing crystal forms, and γ-MnO2 and β-MnO2 mix crystal form most suitable as li-Mn button cell
Positive active material, the discharge capacity of a li-Mn button cell can be greatly improved.Pass through heat treatment, manganese dioxide internal junction
Brilliant water content substantially reduces, and the activity of manganese dioxide can decline because of the presence of its internal crystallization water, this is because knot
Brilliant water makes lithium ion diffusion process in manganese dioxide become slow, when manganese dioxide passes through heat treatment, internal crystallization water content
It substantially reduces, lithium ion diffusion process in manganese dioxide becomes smooth, and battery concentration polarization also mitigates significantly, so it is active
Enhancing, the discharge capacity of battery also accordingly increase.
Specific implementation mode
Illustrate that embodiments of the present invention, those skilled in the art can be by this specification below by way of specific specific example
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
A kind of anode of li-Mn button cell of the present invention, including positive active material manganese dioxide, graphite, acetylene
Black, polytetrafluoroethylene (PTFE), wherein manganese dioxide pass through high-temperature heat treatment, by the α-MnO2 contained inside it and γ-MnO2 crystal knots
Allosteric transformation mixes crystalline structure at γ-MnO2 and β-MnO2, and β-MnO2 crystal forms account for mixing crystal form ratio reach 60-80% it
Between.
Preferably, manganese dioxide is 80-95 parts by weight in the positive active material, and graphite is 1-10 parts by weight, acetylene
Black is 1-5 parts by weight, and polytetrafluoroethylene (PTFE) is 1-5 parts by weight.
It is further preferable that manganese dioxide is 92 parts by weight in the positive active material, graphite is 4 parts by weight, acetylene black
For 2 parts by weight, polytetrafluoroethylene (PTFE) is 2 parts by weight.
A kind of anode preparation method of li-Mn button cell, includes the following steps：
S1:Electrolytic manganese dioxide is sintered 10-20h in sintering furnace under the conditions of 350-440 DEG C；
S2:Sintered manganese dioxide and graphite, acetylene black, polytetrafluoroethylene material are sufficiently mixed；
S3:Being prepared by techniques such as dry mixing, wet-mixing, tabletting, granulation, film-making, dryings becomes positive plate.
The present invention uses the above component, according to conventional li-Mn button cell anode production technology, by dry mixing, and wet-mixing,
Tabletting is granulated, film-making, the techniques such as dry, prepares positive plate of lithium battery, and with cathode lithium, diaphragm is assembled into CR2032 lithium manganese
Button cell.
Inventor during the test, is found surprisingly that the design due to its unique material, proportioning and technique makes this
Invention has the following advantages that：
(1) capacity of battery can significantly increase.By taking CR2032 button cells as an example, cut in constant-resistance 1K ohmic discharges to 2V
It is higher than the lithium battery capacity not through Overheating Treatment manganese dioxide using the capacity of the lithium battery prepared by the present invention only when voltage
50% or so.
(2) internal resistance of battery reduces.By taking CR2032 batteries as an example, the internal resistance ratio of battery is not through Overheating Treatment manganese dioxide
Lithium battery internal resistance low 50% or so.
(3) the high-voltage discharge time increases.
In order to more preferably illustrate the present invention, illustrated with reference to embodiment and comparative example.
Embodiment 1：Electrolytic manganese dioxide is sintered 12h in sintering furnace under the conditions of 375 DEG C, and by sintered titanium dioxide
Manganese presses manganese dioxide: graphite: acetylene black：Polytetrafluoroethylene (PTFE)=92%: 4%: 2%: 2% ratio is sufficiently mixed, by dry mixing,
Wet-mixing, tabletting are granulated, film-making, and prepared by the techniques such as dry become positive plate, using lithium metal as cathode, diaphragm be glass fibre every
Film, 1mol/L lithium perchlorates (LiClO4)/propene carbonate (PC)+glycol dimethyl ether (DME) (volume ratio 1: 1) are electrolysed
Liquid is assembled into CR2032 lithium batteries in the low drying room with -30 degree of dew point.
Embodiment 2：Electrolytic manganese dioxide is sintered 16h in sintering furnace under the conditions of 405 DEG C, and by sintered titanium dioxide
Manganese presses manganese dioxide: graphite: acetylene black：Polytetrafluoroethylene (PTFE)=92%: 4%: 2%: 2% ratio is sufficiently mixed, by dry mixing,
Wet-mixing, tabletting are granulated, film-making, and prepared by the techniques such as dry become positive plate, using lithium metal as cathode, diaphragm be glass fibre every
Film, 1mol/L lithium perchlorates (LiClO4)/propene carbonate (PC)+glycol dimethyl ether (DME) (volume ratio 1: 1) are electrolysed
Liquid is assembled into CR2032 lithium batteries in the low drying room with -30 degree of dew point.
Embodiment 3：Electrolytic manganese dioxide is sintered 20h in sintering furnace under the conditions of 430 DEG C, and by sintered titanium dioxide
Manganese presses manganese dioxide: graphite: acetylene black：Polytetrafluoroethylene (PTFE)=92%: 4%: 2%: 2% ratio is sufficiently mixed, by dry mixing,
Wet-mixing, tabletting are granulated, film-making, and prepared by the techniques such as dry become positive plate, using lithium metal as cathode, diaphragm be glass fibre every
Film, 1mol/L lithium perchlorates (LiClO4)/propene carbonate (PC)+glycol dimethyl ether (DME) (volume ratio 1: 1) are electrolysed
Liquid is assembled into CR2032 lithium batteries in the low drying room with -30 degree of dew point.
Embodiment 4：Electrolytic manganese dioxide is sintered 10h in sintering furnace under the conditions of 350 DEG C, and by sintered titanium dioxide
Manganese presses manganese dioxide: graphite: acetylene black：Polytetrafluoroethylene (PTFE)=92%: 4%: 2%: 2% ratio is sufficiently mixed, by dry mixing,
Wet-mixing, tabletting are granulated, film-making, and prepared by the techniques such as dry become positive plate, using lithium metal as cathode, diaphragm be glass fibre every
Film, 1mol/L lithium perchlorates (LiClO4)/propene carbonate (PC)+glycol dimethyl ether (DME) (volume ratio 1: 1) are electrolysed
Liquid is assembled into CR2032 lithium batteries in the low drying room with -30 degree of dew point.
Embodiment 5：Electrolytic manganese dioxide is sintered 12h in sintering furnace under the conditions of 375 DEG C, and by sintered titanium dioxide
Manganese presses manganese dioxide: graphite: acetylene black：Polytetrafluoroethylene (PTFE)=80%: 10%: 5%: 5% ratio is sufficiently mixed, through overdrying
It mixes, wet-mixing, tabletting, is granulated, film-making, prepared by the techniques such as dry become positive plate, and using lithium metal as cathode, diaphragm is glass fibre
Diaphragm, 1mol/L lithium perchlorates (LiClO4)/propene carbonate (PC)+glycol dimethyl ether (DME) (volume ratio 1: 1) are electrolysed
Liquid is assembled into CR2032 lithium batteries in the low drying room with -30 degree of dew point.
Embodiment 6：Electrolytic manganese dioxide is sintered 16h in sintering furnace under the conditions of 405 DEG C, and by sintered titanium dioxide
Manganese presses manganese dioxide: graphite: acetylene black：Polytetrafluoroethylene (PTFE)=95%: 1%: 3%: 1% ratio is sufficiently mixed, by dry mixing,
Wet-mixing, tabletting are granulated, film-making, and prepared by the techniques such as dry become positive plate, using lithium metal as cathode, diaphragm be glass fibre every
Film, 1mol/L lithium perchlorates (LiClO4)/propene carbonate (PC)+glycol dimethyl ether (DME) (volume ratio 1: 1) are electrolysed
Liquid is assembled into CR2032 lithium batteries in the low drying room with -30 degree of dew point.
Embodiment 7：Electrolytic manganese dioxide is sintered 20h in sintering furnace under the conditions of 430 DEG C, and by sintered titanium dioxide
Manganese presses manganese dioxide: graphite: acetylene black：Polytetrafluoroethylene (PTFE)=90%: 5%: 1%: 4% ratio is sufficiently mixed, by dry mixing,
Wet-mixing, tabletting are granulated, film-making, and prepared by the techniques such as dry become positive plate, using lithium metal as cathode, diaphragm be glass fibre every
Film, 1mol/L lithium perchlorates (LiClO4)/propene carbonate (PC)+glycol dimethyl ether (DME) (volume ratio 1: 1) are electrolysed
Liquid is assembled into CR2032 lithium batteries in the low drying room with -30 degree of dew point.
Embodiment 8：Electrolytic manganese dioxide is sintered 10h in sintering furnace under the conditions of 350 DEG C, and by sintered titanium dioxide
Manganese presses manganese dioxide: graphite: acetylene black：Polytetrafluoroethylene (PTFE)=88%: 6%: 3%: 3% ratio is sufficiently mixed, by dry mixing,
Wet-mixing, tabletting are granulated, film-making, and prepared by the techniques such as dry become positive plate, using lithium metal as cathode, diaphragm be glass fibre every
Film, 1mol/L lithium perchlorates (LiClO4)/propene carbonate (PC)+glycol dimethyl ether (DME) (volume ratio 1: 1) are electrolysed
Liquid is assembled into CR2032 lithium batteries in the low drying room with -30 degree of dew point.
Comparative example 1：By un-sintered manganese dioxide according to manganese dioxide: graphite: acetylene black：Polytetrafluoroethylene (PTFE)=92%: 4%
: 2%: 2% ratio is sufficiently mixed, and by dry mixing, wet-mixing, tabletting is granulated, film-making, and prepared by the techniques such as dry become positive plate,
Using lithium metal as cathode, diaphragm is fibreglass diaphragm, 1mol/L lithium perchlorates (LiClO4)/propene carbonate (PC)+second two
Diethylene glycol dimethyl ether (DME) (volume ratio 1: 1) makees electrolyte, and CR2032 lithium batteries are assembled into the low drying room with -30 degree of dew point.
Comparative example 2：Chinese invention patent CN201710342171.6 discloses a kind of anode material of lithium battery and its preparation
Method, steps are as follows：
Step 1: the preparation of monodisperse fluorinated graphene solution
It it is 15 μm by maximum outside diameter size, the 1g fluorinated graphene nanometer sheets that fluorine carbon ratio is 0.9 dissolve in 19g absolute ethyl alcohols
In, glass bar is put into ultrasonic oscillation device ultrasound after stirring evenly to prepare within 30 minutes uniform monodisperse fluorinated graphene molten
Liquid；
Step 2: the manganese dioxide powder that 5g grain sizes are 30 μm is added to the monodisperse fluorinated graphene that step 1 obtains
In solution, mixed solution is obtained；
Dried Step 3: the mixed solution that step 2 obtains is put into baking oven, drying temperature be 50 DEG C, drying it is same
Shi Jinhang mechanical agitations, until drying；
Step 4: dividing the powder after drying in baking oven, 300 DEG C of constant temperature of progress are heat-treated 20 hours；
Step 5: the powder after step 4 is heat-treated is ground, sieving obtains the lithium that particle diameter distribution is 10~30 μm
Cell positive material.
Above-mentioned positive electrode is passed through into dry mixing, wet-mixing, tabletting is granulated, film-making, and prepared by the techniques such as dry become positive plate,
Using lithium metal as cathode, diaphragm is fibreglass diaphragm, 1mol/L lithium perchlorates (LiClO4)/propene carbonate (PC)+second two
Diethylene glycol dimethyl ether (DME) (volume ratio 1: 1) makees electrolyte, and CR2032 lithium batteries are assembled into the low drying room with -30 degree of dew point.
Comparative example 3：Chinese invention patent CN201210063572.5 discloses a kind of fiber ball-shaped lithium-ion battery anode
Material lithium manganese phosphate and preparation method thereof weighs a certain amount of lithium dihydrogen phosphate and manganese carbonate in proportion, and lithium, manganese, phosphorus is made to rub
You are added into the mixed liquor of deionized water and absolute ethyl alcohol, ball milling 8 while stirring in agitating ball mill than being 1: 1: 1
Hour, then, be separately added into mass percentage be lithium manganese phosphate product 10% polyvinyl alcohol be used as carbon source, addition quality hundred
Divide the ammonium polymethacrylate that content is raw material gross mass 3% as dispersant, continues stirring ball-milling after 10 hours by its turn
Enter in Ultrafine Grinding that ball milling obtains uniform slurry in 8 hours again, which is spray-dried, inlet temperature is 240 DEG C, outlet
Temperature is 65 DEG C, fiber spherical precursor is obtained, by the fiber spherical precursor with 5 DEG C/min of heating in argon gas atmosphere
Speed is heat-treated, and in 450 DEG C of constant temperature calcinings 6 hours in heat treatment process, then in 700 DEG C of constant temperature calcinings 10 hours, is obtained
It is anode with the material to fiber spherical shape lithium ion battery anode material manganese lithium phosphate, using lithium piece as cathode, makes CR2032 types
Button cell.
Battery in embodiment 1-8 and comparative example 1-3 is used into 1K constant-resistance discharges, discharge cut-off voltage 2.0V, 23
Discharge performance is tested in ± 2 DEG C of environment, and the following table 1 is discharge time data.
Table 1
Table 2 is, in 1K constant-resistance discharges, discharge cut-off voltage is 2.0V's by the battery in embodiment 1-8 and comparative example 1-3
Discharge capacity and internal resistance correction data.
Table 2：
| Project | The internal resistance of cell (Ω) | Discharge capacity (mAh) |
| Embodiment 1 | 8.2 | 201.0 |
| Embodiment 2 | 7.8 | 202.3 |
| Embodiment 3 | 7.2 | 207.2 |
| Embodiment 4 | 8.5 | 200.3 |
| Embodiment 5 | 8.0 | 200.0 |
| Embodiment 6 | 7.2 | 204.3 |
| Embodiment 7 | 7.4 | 207.2 |
| Embodiment 8 | 8.4 | 208.3 |
| Comparative example 1 | 12.5 | 142.2 |
| Comparative example 2 | 13.2 | 135.6 |
| Comparative example 3 | 12.8 | 145.6 |
It can be seen that the different positive active material of lithium-manganese cell is by different temperatures and time sintered electric discharge
Performance and capacity all significantly improve.
The explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvement and modification should also be fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to realize or use the present invention.To this
A variety of modifications of a little embodiments will be apparent to those skilled in the art, as defined herein general
Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will not
It can be intended to be limited to the embodiments shown herein, and be to fit to consistent with the principles and novel features disclosed in this article
Widest range.
Claims (10)
1. a kind of anode of li-Mn button cell, it is characterised in that：Including positive active material manganese dioxide, graphite, acetylene black,
Polytetrafluoroethylene (PTFE), wherein manganese dioxide pass through high-temperature heat treatment, and the α-MnO2 contained inside it and γ-MnO2 crystal structures are turned
Become γ-MnO2 and β-MnO2 mixing crystalline structures, and β-MnO2 crystal forms account for the ratio of mixing crystal form and reach between 60-80%.
2. the anode of li-Mn button cell as described in claim 1, it is characterised in that：Titanium dioxide in the positive active material
Manganese is 80-95 parts by weight, and graphite is 1-10 parts by weight, and acetylene black is 1-5 parts by weight, and polytetrafluoroethylene (PTFE) is 1-5 parts by weight.
3. the anode of li-Mn button cell as claimed in claim 1 or 2, it is characterised in that：Two in the positive active material
Manganese oxide is 92 parts by weight, and graphite is 4 parts by weight, and acetylene black is 2 parts by weight, and polytetrafluoroethylene (PTFE) is 2 parts by weight.
4. a kind of anode preparation method of li-Mn button cell, which is characterized in that include the following steps：
S1:Electrolytic manganese dioxide is sintered 10-20h in sintering furnace under the conditions of 350-440 DEG C；
S2:Sintered manganese dioxide and graphite, acetylene black, polytetrafluoroethylene material are sufficiently mixed；
S3:Being prepared by techniques such as dry mixing, wet-mixing, tabletting, granulation, film-making, dryings becomes positive plate.
5. the anode preparation method of li-Mn button cell as claimed in claim 4, it is characterised in that：General in the step S1
Electrolytic manganese dioxide is sintered 12h in sintering furnace under the conditions of 375 DEG C.
6. the anode preparation method of li-Mn button cell as claimed in claim 4, it is characterised in that：General in the step S1
Electrolytic manganese dioxide is sintered 16h in sintering furnace under the conditions of 405 DEG C.
7. the anode preparation method of li-Mn button cell as claimed in claim 4, it is characterised in that：General in the step S1
Electrolytic manganese dioxide is sintered 20h in sintering furnace under the conditions of 440 DEG C.
8. the anode preparation method of li-Mn button cell as claimed in claim 4, it is characterised in that：General in the step S1
Electrolytic manganese dioxide is sintered 10h in sintering furnace under the conditions of 350 DEG C.
9. the anode preparation method of the li-Mn button cell as described in claim 4-8 is any, it is characterised in that：The step S2
It is middle by manganese dioxide according to 80-95 parts by weight, graphite 1-10 parts by weight, acetylene black 1-5 parts by weight, polytetrafluoroethylene (PTFE) 1-5 weight
Part is sufficiently mixed.
10. the anode preparation method of the li-Mn button cell as described in claim 4-9 is any, it is characterised in that：The step
By manganese dioxide according to 92 parts by weight in S2,4 parts by weight of graphite, 2 parts by weight of acetylene black, 2 parts by weight of polytetrafluoroethylene (PTFE) are fully mixed
It closes.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109148822A (en) * | 2018-09-30 | 2019-01-04 | 中国航发北京航空材料研究院 | A kind of high-capacity lithium ion battery primary battery anode |
| CN109585777A (en) * | 2018-12-06 | 2019-04-05 | 福建南平南孚电池有限公司 | A kind of li-Mn button cell anode piece preparation method improving heavy-current discharge capacity |
| CN109728243A (en) * | 2018-12-06 | 2019-05-07 | 福建南平南孚电池有限公司 | A kind of positive pole of lithium manganese battery manufacture craft |
| CN112838188A (en) * | 2021-02-03 | 2021-05-25 | 常州宇峰电池有限公司 | Manufacturing method of storage-resistant lithium-manganese battery positive electrode |
| CN113140846A (en) * | 2021-04-16 | 2021-07-20 | 武汉孚安特科技有限公司 | Lithium-manganese battery and manufacturing method thereof |
| WO2023102778A1 (en) * | 2021-12-08 | 2023-06-15 | Medtrum Technologies Inc. | Positive electrode plate for medical device battery and its preparation method |
| CN116632247A (en) * | 2023-07-20 | 2023-08-22 | 珠海市冠力电池有限公司 | Lithium manganese button cell positive electrode material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4133856A (en) * | 1976-09-29 | 1979-01-09 | Sanyo Electric Co., Ltd. | Process for producing a positive electrode for a non-aqueous cell |
| CN1189809A (en) * | 1995-06-07 | 1998-08-05 | 杜拉塞尔公司 | Improved manganese dioxide for lithium batteries |
| CN1588681A (en) * | 2004-10-13 | 2005-03-02 | 惠州市德赛能源科技有限公司 | Needle shape lithium-manganese dioxide cell and its producing method |
| 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 |
| CN106602073A (en) * | 2016-12-21 | 2017-04-26 | 惠州亿纬锂能股份有限公司 | Composite binder for lithium battery and application of composite binder |
-
2018
- 2018-03-13 CN CN201810203179.9A patent/CN108493444A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4133856A (en) * | 1976-09-29 | 1979-01-09 | Sanyo Electric Co., Ltd. | Process for producing a positive electrode for a non-aqueous cell |
| CN1189809A (en) * | 1995-06-07 | 1998-08-05 | 杜拉塞尔公司 | Improved manganese dioxide for lithium batteries |
| CN1588681A (en) * | 2004-10-13 | 2005-03-02 | 惠州市德赛能源科技有限公司 | Needle shape lithium-manganese dioxide cell and its producing method |
| 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 |
| CN106602073A (en) * | 2016-12-21 | 2017-04-26 | 惠州亿纬锂能股份有限公司 | Composite binder for lithium battery and application of composite binder |
Non-Patent Citations (3)
| Title |
|---|
| 林凤儿: "浅谈Li-MnO2电池的制造工艺", 《电池工业》 * |
| 郭学益等: "二氧化锰晶型转变研究", 《矿冶工程》 * |
| 陈川等: "锂锰电池正极的制备及其性能", 《电池》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109148822A (en) * | 2018-09-30 | 2019-01-04 | 中国航发北京航空材料研究院 | A kind of high-capacity lithium ion battery primary battery anode |
| CN109585777A (en) * | 2018-12-06 | 2019-04-05 | 福建南平南孚电池有限公司 | A kind of li-Mn button cell anode piece preparation method improving heavy-current discharge capacity |
| CN109728243A (en) * | 2018-12-06 | 2019-05-07 | 福建南平南孚电池有限公司 | A kind of positive pole of lithium manganese battery manufacture craft |
| CN109728243B (en) * | 2018-12-06 | 2021-05-14 | 福建南平南孚电池有限公司 | Manufacturing process of lithium-manganese battery positive electrode |
| CN109585777B (en) * | 2018-12-06 | 2022-02-18 | 福建南平南孚电池有限公司 | Preparation method of lithium-manganese button cell positive plate for improving large-current discharge capacity |
| CN112838188A (en) * | 2021-02-03 | 2021-05-25 | 常州宇峰电池有限公司 | Manufacturing method of storage-resistant lithium-manganese battery positive electrode |
| CN113140846A (en) * | 2021-04-16 | 2021-07-20 | 武汉孚安特科技有限公司 | Lithium-manganese battery and manufacturing method thereof |
| WO2023102778A1 (en) * | 2021-12-08 | 2023-06-15 | Medtrum Technologies Inc. | Positive electrode plate for medical device battery and its preparation method |
| CN116632247A (en) * | 2023-07-20 | 2023-08-22 | 珠海市冠力电池有限公司 | Lithium manganese button cell positive electrode material and preparation method and application thereof |
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