CN108428859A - A method of preparing lithium thionyl chloride cell cathode - Google Patents
A method of preparing lithium thionyl chloride cell cathode Download PDFInfo
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- CN108428859A CN108428859A CN201810296028.2A CN201810296028A CN108428859A CN 108428859 A CN108428859 A CN 108428859A CN 201810296028 A CN201810296028 A CN 201810296028A CN 108428859 A CN108428859 A CN 108428859A
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- thionyl chloride
- cell cathode
- lithium thionyl
- chloride cell
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- 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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of methods preparing lithium thionyl chloride cell cathode, the difference is that, solvent and 60% ptfe emulsion are mixed, obtain mixed liquor, it is stirred after acetylene black, conductive agent and ammonium hydrogen carbonate mixing are added in the mixed liquor, slurry is obtained, then cell cathode is prepared into after the slurry is carried out fiber pore-creating.Simple production process of the present invention, raw material cost is low, and all process steps are achieved in former process；The average empty radius of actual measurement increases 11.04%, and most probable pore size increases 63.3%；Significantly improve the performance for improving lithium thionyl chloride cell multiplying power discharging.
Description
Technical field
The present invention relates to lithium thionyl chloride cell fields, and in particular to a kind of side preparing lithium thionyl chloride cell cathode
Method.
Background technology
Lithium thionyl chloride cell is battery more highest than energy, discharging voltage balance, temperature in use in current electrochmical power source
Reachable -55 DEG C~+85 DEG C, storage life be up to 10 years, in armies such as military weapons, geological prospecting, instrument and meter, Internet of Things facilities
It is all widely used in thing and civilian industry.But conventional lithium thionyl chloride cell, in storage and discharge process, carbon is cloudy
Pole surface gradually loses activity because of the deposition of LiCl, and cathode reaction resistance increases, and the current output capability of battery is caused to decline,
It there is safety issue, voltage delay and current output capability, research is found can be with by the quality that improves carbon cathode
Effectively improve the performance of lithium thionyl chloride cell.
The production method of existing lithium thionyl chloride cell cathode：A certain proportion of deionized water, ethyl alcohol, binder is first
Row mixing, is then added a certain proportion of acetylene black, conductive agent is stirred, and the baking then carried out at 180 DEG C is subject to other
Process is made.The battery carbon cathode internal capillary of existing manufacture craft production is mainly generated by binder high temperature fiberisation
Space networks, moisture evaporation, ethyl alcohol volatilize pore-creating, there are micropore average pore size is less than normal, the less problem of big pore size distribution, so as to cause
Carbon cathode is easily deposited by LiCl and is blocked, and cathode reaction resistance increases, and battery current fan-out capability is caused to decline even battery failure
The case where occur.
Invention content
In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides one kind can effectively improve lithium thionyl chloride cell
The cathode manufacturing method of cathode diameter macropores and distribution ratio.
The technical solution adopted in the present invention is：
A method of lithium thionyl chloride cell cathode is prepared, the difference is that, by solvent and 60% polytetrafluoro
Vac emulsion is mixed, and mixed liquor is obtained, and is stirred after acetylene black, conductive agent and ammonium hydrogen carbonate mixing are added in the mixed liquor
It mixes, obtains slurry, then cell cathode is prepared into after the slurry is carried out fiber pore-creating.
In above-mentioned technical proposal, the cell cathode is power-type lithium thionyl chloride cell cathode or capacity type lithium-thionyl acyl
Chlorine cell cathode.
In above-mentioned technical proposal, the solvent is one or both of deionized water or absolute ethyl alcohol.
In above-mentioned technical proposal, the power-type lithium thionyl chloride cell cathode includes the following steps：
A:Prepare powder：Solvent and 60% ptfe emulsion are mixed, mixed liquor is obtained；In the mixed liquor
It is stirred after middle addition acetylene black, conductive agent and ammonium hydrogen carbonate mixing, obtains slurry；
B:Fiber pore-creating：Slurry described in step A is subjected to fibrosis pore-creating, the first powder is obtained after pore-creating；
C:Prepare cathode：First powder ethyl alcohol described in step B or isopropanol are impregnated, the second powder is obtained；
D：Make diaphragm：Second powder described in step C is gradually rolled into diaphragm；
E：Diaphragm bonds：Diaphragm described in step D is bonded to nickel screen two sides, it is cloudy to be fabricated to power-type lithium thionyl chloride cell
Pole.
In above-mentioned technical proposal, which is characterized in that the capacity type lithium thionyl chloride cell cathode includes the following steps：
a:Prepare powder：Solvent and 60% ptfe emulsion are mixed, mixed liquor is obtained；In the mixed liquor
It is stirred after middle addition acetylene black, conductive agent and ammonium hydrogen carbonate mixing, obtains slurry；
b:Make cathode particles：Slurry described in step a is produced into cathode particles；
c：Fibrosis pore-creating：Cathode particles described in step c are subjected to fibrosis pore-creating, it is sub- that capacity type lithium is obtained after pore-creating
Chlorosulfuric acid cell cathode.
In above-mentioned technical proposal, the temperature of the fiber pore-creating is 180 DEG C.
Compared with prior art, the beneficial effects of the invention are as follows：Simple production process, raw material cost is low, all process steps
It is achieved in former process；The average empty radius of actual measurement increases 11.04%, and most probable pore size increases 63.3%；Obviously
Improve the performance for improving lithium thionyl chloride cell multiplying power discharging.
Description of the drawings
Fig. 1 is the ER18505M battery room temperatures that the ER18505M batteries that the prior art makes make with the technology of the present invention
400mA discharge curves compare；
Embodiment ER18505M batteries can promote 9.6% discharge capacity of the cell in 400mA constant currents, and improve
Load voltage, hence it is evident that improve cell cathode passivation.
Fig. 2 is that the ER14250 batteries that the ER14250 batteries that the prior art makes make with the technology of the present invention are deposited at 60 DEG C
It puts 180 days, the curve comparison that then 10mA discharges at room temperature；
ER14250 batteries store 180 days batteries at 60 DEG C, are discharged with 10mA, 3 hours 42 comparative example battery used time
Minute is restored to normal voltage, and embodiment 40 seconds battery used times of production are restored to normal voltage, significant effect.
Specific implementation mode
This programme is described in detail with reference to specific embodiment and attached drawing.
1%~5% ammonium hydrogen carbonate of acetylene black weight is added in the slurry, ammonium hydrogencarbonate is heated easily to be decomposed, and ammonia is generated
Gas (NH3), water (H2O), carbon dioxide (CO2).Chemical equation is：NH4HCO3=NH3↑+H2O+CO2↑), the gas of generation can
To play the role of expanding aperture, to promote the functional effect of entire lithium thionyl chloride cell cathode.All reaction products are all
Because of vaporization at high temperature, generated exhaust gas is recycled using weak acid water, avoids pollution air, nothing is appointed in lithium thionyl chloride cell cathode
What is remained.
Example one：The preparation of power-type lithium thionyl chloride cell ER18505M cathodes
1. according to acetylene black：Binder：Absolute ethyl alcohol：Conductive agent：Deionized water：Ammonium hydrogencarbonate=600g：60mL：
200mL：60g：8kg：The dosage of 12g claims (amount) to take, and first liquid charging stock is mixed, solid material is then added, in blender
Stirring at low speed 20 minutes obtains slurry；
2. slurry uniformly in tiling to stainless steel material disc, is put in fibrosis 18 hours in 180 DEG C of convection ovens, obtain
First powder；
3. the first powder powder ethyl alcohol or isopropanol impregnate 2~3 minutes, the second powder is obtained；
4. by step, 3. second powder is gradually rolled into twin rollers the diaphragm of required thickness several times, not higher than
Naturally dry in 60 DEG C of environment；
5. by step, 4. the diaphragm is bonded to nickel screen two sides by binder, is fabricated to power-type lithium thionyl chloride cell
Cathode.
6. making ER18505M batteries and carrying out 400mA constant-current discharges at room temperature.
Example two：The preparation of capacity type lithium thionyl chloride cell ER14250 cathodes
1. according to acetylene black：Binder：Absolute ethyl alcohol：Conductive agent：Ammonium hydrogencarbonate=1000g：56mL：6000mL：40g：
The dosage of 35g claims (amount) to take, and first liquid charging stock is mixed, solid material is then added, stirring at low speed 20 minutes in blender,
Obtain slurry；
2. by step 1. the slurry be put in extruder squeeze out homogeneous diameter bar；By bar be placed in high speed from
In scheming, round or ellipse cathode particles are produced using centrifugal force；
3. by step, 2. the graininess cathode is then fine in 180 DEG C of convection ovens as drying 24 hours at 60 DEG C
Dimensionization pore-creating in 10 hours obtains capacity type lithium thionyl chloride cell cathode after pore-creating；
4. making ER14250 batteries, placed 180 days at 60 DEG C, 10mA constant-current discharges are used after being cooled to room temperature.
The preparation of one power-type lithium thionyl chloride cell ER18505M cathodes of comparative example
1. according to acetylene black：Binder：Absolute ethyl alcohol：Conductive agent：Deionized water=600g：60mL：200mL：60g：8kg
Dosage claim (amount) to take, first liquid charging stock is mixed, solid material is then added, stirring at low speed 20 minutes, are obtained in blender
Take slurry；
2. slurry uniformly in tiling to stainless steel material disc, is put in fibrosis 18 hours in 180 DEG C of convection ovens, obtain
First powder；
3. the first powder powder ethyl alcohol or isopropanol impregnate 2~3 minutes, the second powder is obtained；
4. by step, 3. second powder is gradually rolled into twin rollers the diaphragm of required thickness several times, not higher than
Naturally dry in 60 DEG C of environment；
5. by step, 4. the diaphragm is bonded to nickel screen two sides by binder, is fabricated to power-type lithium thionyl chloride cell
Cathode.
6. making ER18505M batteries and carrying out 400mA constant-current discharges at room temperature.
The preparation of two capacity type lithium thionyl chloride cell ER14250 cathodes of comparative example
1. according to acetylene black：Binder：Absolute ethyl alcohol：Conductive agent=1000g：56mL：6000mL：The dosage of 40g claims
(amount) takes, and first liquid charging stock is mixed, solid material is then added, and stirring at low speed 20 minutes in blender obtain slurry；
2. by step 1. the slurry be put in extruder squeeze out homogeneous diameter bar；By bar be placed in high speed from
In scheming, round or ellipse cathode particles are produced using centrifugal force；
3. by step, 2. the graininess cathode is then fine in 180 DEG C of convection ovens as drying 24 hours at 60 DEG C
Dimensionization pore-creating in 10 hours obtains capacity type lithium thionyl chloride cell cathode after pore-creating；
4. making ER14250 batteries, placed 180 days at 60 DEG C, 10mA constant-current discharges are used after being cooled to room temperature.
1 different disposal ER14250 particle parameters of table
Adsorbed gas is nitrogen in table, and as can be seen from Table 1, through ammonium hydrogen carbonate, treated that aperture has compared to contrast groups
Expand.
The protection domain of these examples being not intended to limit the present invention with the present invention is merely to illustrate.In addition, reading
After the technology contents of the present invention, those skilled in the art can make the present invention various changes, modification or modification, all this
A little equivalent forms also belong within the required protection domain limited of the application.
Claims (6)
1. a kind of method preparing lithium thionyl chloride cell cathode, which is characterized in that by solvent and 60% ptfe emulsion
It is mixed, obtains mixed liquor, stirred, obtain after acetylene black, conductive agent and ammonium hydrogen carbonate mixing are added in the mixed liquor
Slurry, then it is prepared into cell cathode after the slurry high-temperature process is carried out fiber pore-creating.
2. a kind of method preparing lithium thionyl chloride cell cathode according to claim 1, which is characterized in that the battery is cloudy
Extremely power-type lithium thionyl chloride cell cathode or capacity type lithium thionyl chloride cell cathode.
3. a kind of method preparing lithium thionyl chloride cell cathode according to claim 1, which is characterized in that the solvent is
One or both of deionized water or absolute ethyl alcohol.
4. a kind of method preparing lithium thionyl chloride cell cathode according to claim 2, which is characterized in that the power-type
Lithium thionyl chloride cell cathode includes the following steps：
A:Prepare powder：Solvent and 60% ptfe emulsion are mixed, mixed liquor is obtained；Add in the mixed liquor
It is stirred after entering acetylene black, conductive agent and ammonium hydrogen carbonate mixing, obtains slurry；
B:Fiber pore-creating：Slurry described in step A is subjected to fibrosis pore-creating, the first powder is obtained after pore-creating；
C:Prepare cathode：First powder ethyl alcohol described in step B or isopropanol are impregnated, the second powder is obtained；
D：Make diaphragm：Second powder described in step C is gradually rolled into diaphragm；
E：Diaphragm bonds：Diaphragm described in step D is bonded to nickel screen two sides, is fabricated to power-type lithium thionyl chloride cell cathode.
5. a kind of method preparing lithium thionyl chloride cell cathode according to claim 2, which is characterized in that the capacity type
Lithium thionyl chloride cell cathode includes the following steps：
a:Prepare powder：Solvent and 60% ptfe emulsion are mixed, mixed liquor is obtained；Add in the mixed liquor
It is stirred after entering acetylene black, conductive agent and ammonium hydrogen carbonate mixing, obtains slurry；
b:Make cathode particles：Slurry described in step a is produced into cathode particles；
c：Fibrosis pore-creating：Cathode particles described in step c are subjected to fibrosis pore-creating, capacity type lithium-thionyl acyl is obtained after pore-creating
Chlorine cell cathode.
6. a kind of method preparing lithium thionyl chloride cell cathode according to claim 1, which is characterized in that the fiber is made
The temperature in hole is 180 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110690450A (en) * | 2019-10-24 | 2020-01-14 | 惠州亿纬锂能股份有限公司 | Carbon electrode and forming method and application thereof |
| CN111081974A (en) * | 2019-12-14 | 2020-04-28 | 陕西煤业化工技术研究院有限责任公司 | Lithium thionyl chloride battery cathode piece containing asphalt coke activated carbon catalytic material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110690450A (en) * | 2019-10-24 | 2020-01-14 | 惠州亿纬锂能股份有限公司 | Carbon electrode and forming method and application thereof |
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| CN111081974A (en) * | 2019-12-14 | 2020-04-28 | 陕西煤业化工技术研究院有限责任公司 | Lithium thionyl chloride battery cathode piece containing asphalt coke activated carbon catalytic material and preparation method thereof |
| CN111081974B (en) * | 2019-12-14 | 2021-11-23 | 陕西煤业化工技术研究院有限责任公司 | Lithium thionyl chloride battery cathode piece containing asphalt coke activated carbon catalytic material and preparation method thereof |
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Application publication date: 20180821 |