CN112331849A - Lithium thionyl chloride battery positive electrode material and application thereof - Google Patents
Lithium thionyl chloride battery positive electrode material and application thereof Download PDFInfo
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- CN112331849A CN112331849A CN202011191462.8A CN202011191462A CN112331849A CN 112331849 A CN112331849 A CN 112331849A CN 202011191462 A CN202011191462 A CN 202011191462A CN 112331849 A CN112331849 A CN 112331849A
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- SOZVEOGRIFZGRO-UHFFFAOYSA-N [Li].ClS(Cl)=O Chemical compound [Li].ClS(Cl)=O SOZVEOGRIFZGRO-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000839 emulsion Substances 0.000 claims abstract description 31
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 30
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 30
- 239000006229 carbon black Substances 0.000 claims abstract description 29
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 26
- 239000006230 acetylene black Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000007873 sieving Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 28
- 239000000843 powder Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000006258 conductive agent Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 206010016654 Fibrosis Diseases 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000004761 fibrosis Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011802 pulverized particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
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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
- H01M4/06—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
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- General Chemical & Material Sciences (AREA)
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- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a lithium thionyl chloride battery positive electrode material and application thereof, wherein the positive electrode material comprises acetylene black, superconducting carbon black, absolute ethyl alcohol, deionized water and polytetrafluoroethylene emulsion, the mass ratio of the acetylene black, the superconducting carbon black, the absolute ethyl alcohol, the deionized water to the polytetrafluoroethylene emulsion is 10 (0.1-0.5) to (1.0-3) to (15-25) to (0.5-1.0), the positive electrode material is mixed by a high-speed mixer, and a positive electrode plate is obtained by sieving, fiberizing, pressing and slitting.
Description
Technical Field
The invention belongs to a lithium thionyl chloride battery, and relates to a lithium thionyl chloride battery positive electrode material and application thereof.
Background
Since the development of inorganic non-aqueous electrolyte lithium thionyl chloride batteries started from GTE company in 1971 to nearly half a century nowadays, lithium thionyl chloride batteries are well paid attention to the field of military industry due to the characteristics of high specific energy, stable working voltage, long service life, wide use temperature range (-40 ℃ -85 ℃) and the like, and are used as a matched power supply in weapon development of many countries. In recent years, countries such as china, the united states of america, france, israel and the like have further strengthened technical research on the battery system, and the application of the battery system is expected to be expanded to a wider civil field.
At present, the lithium thionyl chloride battery is widely applied to special industries such as intelligent water meters, electric meters, gas meters, oil exploration and other low-power consumption industrial equipment. However, the battery is easy to lose efficacy after being stored at high temperature for a period of time, the phenomenon of serious voltage lag occurs, the safety performance is not ideal enough, and the reliability of the battery is influenced.
CN105932239A discloses a positive electrode material of a lithium thionyl chloride battery and a preparation method thereof. The positive electrode material is prepared by processing acetylene black, copper powder, polytetrafluoroethylene emulsion and pure water through multiple processes, the positive electrode material with uniform granularity can be obtained through the steps of scattering and screening, the lithium thionyl chloride battery produced by using the positive electrode material is stable in performance, but the metal copper powder is used as a conductive agent, electrons are transmitted through the metal material, belong to homogeneous transmission and can form voltage difference, the heat generated by the voltage difference formed by the transmission of the electronic conductive agent is increased, and the output capacity of the battery is reduced.
CN103236516A discloses a method for preparing a high-temperature battery anode, which comprises the steps of mixing, shot blasting, carbon packet extruding, drying, fiber forming, crushing and infiltrating, net surfing, rolling, fiber forming, molding and the like, wherein a carbon sheet can be finely pressed to a proper process size according to batteries of different types, the prepared battery anode can significantly improve the high-temperature performance of a lithium thionyl chloride battery, and the preparation process is tedious, difficult to operate and difficult to realize continuous production.
The lithium thionyl chloride battery positive electrode in the scheme has the defects of low battery output capacity, complex manufacturing process and the like, so that the development of the lithium thionyl chloride battery positive electrode which is simple to manufacture and high in battery discharge capacity is necessary.
Disclosure of Invention
The invention aims to provide a lithium thionyl chloride battery positive electrode material and application thereof, in particular to a lithium thionyl chloride battery positive electrode with high liquid absorption rate and large discharge capacity, which is used for improving the reliability and environmental adaptability of a lithium thionyl chloride battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a lithium thionyl chloride battery positive electrode material, which comprises acetylene black, superconducting carbon black, absolute ethyl alcohol, deionized water and Polytetrafluoroethylene (PTFE) emulsion;
the mass ratio of the acetylene black, the superconducting carbon black, the absolute ethyl alcohol, the deionized water and the PTFE emulsion is 10 (0.1-0.5): (1.0-3.0): 15-25): 0.5-1.0), for example: 10:0.1:1.0:15:0.5, 10:0.2:2:20:0.8, 10:0.5:3.0:25:1.0, 10:0.3:1.5:20:1.0, 10:0.2:1.5:20:1.0, or 10:0.3:2:20:0.8, etc.
The lithium thionyl chloride battery positive electrode material does not contain a metal conductive agent, electrons are transmitted through the carbon material, heterogeneous transmission is achieved, no voltage difference is formed, heat generated by the voltage difference formed by the transmission of the electrons through the metal conductive agent is reduced, and the output capacity of the battery is improved.
By adopting the mass ratio, the invention can ensure that the positive electrode has higher porosity and better liquid absorption and retention effects.
Preferably, the mass ratio of the acetylene black, the superconducting carbon black, the absolute ethyl alcohol, the deionized water and the polytetrafluoroethylene emulsion is 10 (0.2-0.5): 2-3): 20-25): 0.8-1.0, and preferably 10:0.2:2:20: 0.8.
Preferably, the superconducting carbon black is any one or a combination of at least two of powdered N472, EC300JD or Vulcan XC-72, preferably Vulcan XC-72.
Preferably, the particle size of the superconducting carbon black is 20-30 nm, such as: 20nm, 21nm, 22nm, 23nm, 24nm, 25nm, 26nm, 27nm, 28nm, 29nm, or 30 nm.
Preferably, the polytetrafluoroethylene emulsion is an aqueous emulsion with the mass fraction of 50-70%, such as: 50%, 55%, 60%, 65%, 70%, etc., preferably 60% aqueous emulsion.
In a second aspect, the invention provides a lithium thionyl chloride battery positive electrode plate, which comprises the lithium thionyl chloride battery positive electrode material as described in the first aspect.
In a third aspect, the invention provides a preparation method of the positive electrode plate of the lithium thionyl chloride battery in the second aspect, and the preparation method comprises the following steps:
(1) mixing acetylene black, superconducting carbon black, absolute ethyl alcohol, deionized water and polytetrafluoroethylene emulsion according to a ratio to obtain a paste material;
(2) and (2) drying, crushing, filtering, fiberizing, extruding and cutting the paste material obtained in the step (1) in sequence to obtain the lithium thionyl chloride battery positive pole piece.
Preferably, the mixing in step (1) specifically comprises:
(a) mixing acetylene black and superconducting carbon black to obtain a mixture;
(b) wet mixing the mixture obtained in the step (a) by using absolute ethyl alcohol and deionized water to obtain a wet material;
(c) adding the polytetrafluoroethylene emulsion into the wet material obtained in the step (b), and continuously stirring to obtain a paste material.
Preferably, the mixing in step (1) is carried out using a high-speed stirrer.
According to the preparation method of the carbon anode piece of the lithium thionyl chloride battery, acetylene black and superconducting carbon black are uniformly mixed by adopting a high-speed stirrer, so that the powder is uniformly dispersed and uniformly mixed at multiple angles.
Preferably, the mixing speed of the step (a) is 20-30 r/min, such as: 20r/min, 21r/min, 22r/min, 23r/min, 24r/min, 25r/min, 26r/min, 27r/min, 28r/min, 29r/min or 30r/min, etc., preferably 25 r/min.
Preferably, the mixing time is 0.5-1.5 h, such as: 0.5h, 0.7h, 0.9h, 1h, 1.3h or 1.5h, etc., preferably 1 h.
Preferably, the stirring speed of the wet mixing in the step (b) is 25 to 35r/min, for example: 25r/min, 27r/min, 30r/min, 32r/min, 35r/min, etc., preferably 30 r/min.
Preferably, the time of wet mixing and stirring is 25-35 min, for example: 25min, 27min, 30min, 32min or 35min, preferably 30 min.
Preferably, the speed of stirring after adding the polytetrafluoroethylene emulsion in the step (c) is 3 to 8r/min, for example: 3r/min, 4r/min, 5r/min, 6r/min, 7r/min or 8r/min, etc., preferably 5 r/min.
Preferably, the time for continuing stirring is 8-12 min, for example: 8min, 9min, 10min, 11min or 12min, etc., preferably 10 min.
The polytetrafluoroethylene emulsion is added at last, and the low-speed stirring paddle is started, so that the high-speed demulsification of the polytetrafluoroethylene in the alcohol solution can be effectively prevented.
Preferably, the drying temperature of the paste material in the step (2) is 50-70 ℃, for example: 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃ and the like.
Preferably, the drying time of the paste material in the step (2) is 10-14 h, for example: 10h, 11h, 12h, 13h or 14h, etc., preferably 12 h.
Preferably, the filtering device in step (2) comprises a filtering screen.
Preferably, the mesh number of the filter screen is 150-250 meshes, such as: 150 mesh, 160 mesh, 180 mesh, 200 mesh, 220 mesh, 250 mesh, etc., preferably 200 mesh.
The positive electrode of the invention has uniform particle size, and the prepared carbon positive electrode is more uniform, so the consistency of the battery performance is better.
Preferably, the fiberization treatment described in step (2) is carried out in an oven.
Preferably, the temperature of the fiberization treatment in the step (2) is 250-350 ℃, for example: 250 ℃, 260 ℃, 280 ℃, 300 ℃, 320 ℃ or 350 ℃, and the like, preferably 300 ℃.
Preferably, the time of the fiberization treatment in the step (2) is 1.5-2.5 h, for example: 1.5h, 1.6h, 1.8h, 2.0h, 2.3h or 2.5h, etc., preferably 2 h.
As a preferred technical scheme, the preparation method of the positive pole piece of the lithium thionyl chloride battery comprises the following steps:
(1') mixing acetylene black and superconducting carbon black in a high-speed mixer with the mixing speed of 20-30 r/min for 0.5-1.5 h to obtain a mixture;
(2 ') carrying out wet mixing on the mixture obtained in the step (1') by using absolute ethyl alcohol and deionized water, wherein the stirring speed of the wet mixing is 25-35 r/min, and the stirring time is 25-35 min to obtain a wet material;
(3 ') adding polytetrafluoroethylene emulsion into the wet material obtained in the step (2'), and continuously stirring for 8-12 min at a stirring speed of 3-8 r/min to obtain a paste material;
(4 ') drying the paste material obtained in the step (3') in a drying oven at the temperature of 50-70 ℃ for 10-14 h;
(5 ') putting the dried paste material in the step (4') into a crusher to be crushed and sieving the crushed paste material with a sieve of 150-250 meshes to obtain particles with uniform particle size;
(6 ') placing the filtered particles obtained in the step (5') into an oven at the temperature of 250-350 ℃ for fiberization for 1.5-2.5 h;
(7 ') placing the fibrillated particles obtained in the step (6') into a carbon bag forming machine, and carrying out extrusion forming to obtain a positive carbon bag;
(8 ') cutting the positive electrode carbon bag obtained in the step (7') by using a slitting knife to obtain the positive electrode piece of the lithium thionyl chloride battery.
In a fourth aspect, the invention further provides a lithium thionyl chloride battery, which contains the lithium thionyl chloride battery positive electrode plate as described in the second aspect.
Compared with the prior art, the invention has the following beneficial effects: ,
(I) the lithium thionyl chloride battery positive electrode material does not contain a metal conductive agent, reduces heat generated by voltage difference formed by electron transmission through the metal conductive agent, and improves the output capacity of the battery.
(II) the lithium thionyl chloride battery positive electrode material adopts a proper proportion to prepare raw materials, so that positive electrode particles have larger specific surface area, liquid absorption amount is larger, electrochemical reaction is more sufficient, the utilization rate of active substances is higher, and the battery discharge capacity is larger under the same condition.
Drawings
Fig. 1 is a positive electrode molding carbon package structure provided in embodiment 1 of the present invention;
FIG. 2 is a positive shaped carbon packet structure provided in comparative example 5;
FIG. 3 is a distribution diagram of the particle size of the pulverized particles provided in example 1 of the present invention, wherein 1 is the particle size point and 2 is the content;
fig. 4 is a discharge curve diagram of the batteries of example 1 and ER34615 (type D) according to the present invention, 3 is a discharge curve of the battery finished product prepared in example 1, and 4 is a discharge curve of the battery of ER34615 (type D).
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The "parts" referred to below are all "parts by mass".
Example 1
The embodiment provides a lithium thionyl chloride battery positive pole piece, and a preparation method of the lithium thionyl chloride battery positive pole piece comprises the following steps:
(1) adding 10 parts of acetylene black and 0.2 part of superconducting carbon black into a high-speed stirrer to carry out dry material mixing to obtain a dry material, wherein the stirring speed is 25r/min, and the stirring time is 1 hour; then adding 2 parts of absolute ethyl alcohol and 20 parts of deionized water into the dry material for wet mixing to obtain a wet material, wherein the stirring speed is 30r/min, and the stirring time is 30 minutes; adding 0.8 part of PTFE emulsion into the mixed wet material, and continuously stirring to obtain powder, wherein the stirring speed is 5r/min, and the stirring time is 10 minutes to obtain paste powder;
(2) the paste powder obtained in the step (1) is placed into a drying room at 65 ℃ after being disbursed, dried for 12 hours and naturally cooled after the drying is finished;
(3) pouring the dried powder material dried in the step (2) into a grinder, grinding, sieving by a 200-mesh sieve, performing fibrosis at 300 ℃ for 2 hours, and naturally cooling, wherein the particle size distribution is shown in figure 3;
(4) and (4) sequentially putting the powder obtained in the step (3) into a carbon bag forming machine, extruding into a cylindrical carbon rod shown in figure 1, and cutting into positive pole pieces by using a cutting knife.
Example 2
The embodiment provides a lithium thionyl chloride battery positive pole piece, and a preparation method of the lithium thionyl chloride battery positive pole piece comprises the following steps:
(1) adding 10 parts of acetylene black and 0.3 part of superconducting carbon black into a high-speed stirrer to carry out dry material mixing to obtain a dry material, wherein the stirring speed is 27r/min, and the stirring time is 1.2 hours; then adding 1.5 parts of absolute ethyl alcohol and 18 parts of deionized water into the dry material for wet mixing to obtain a wet material, wherein the stirring speed is 28r/min, and the stirring time is 30 minutes; adding 0.9 part of PTFE emulsion into the mixed wet material, and continuously stirring to obtain powder, wherein the stirring speed is 7r/min, and the stirring time is 10 minutes to obtain paste powder;
(2) the paste powder obtained in the step (1) is placed into a drying room at 60 ℃ after being disbursed, dried for 14 hours and naturally cooled after the drying is finished;
(3) pouring the dried powder material dried in the step (2) into a grinder, grinding, sieving by a 220-mesh sieve, and naturally cooling after fiberization for 2 hours at 330 ℃;
(4) and (4) sequentially putting the powder obtained in the step (3) into a carbon bag forming machine, extruding the powder into cylindrical carbon rods, and cutting the carbon rods into positive pole pieces by using a cutting knife.
Example 3
This example differs from example 1 only in that the amount of the superconducting carbon black added in step (1) is 0.1 part, and other parameters and conditions are exactly the same as those in example 1.
Example 4
This example differs from example 1 only in that the amount of the superconducting carbon black added in step (1) is 0.5 parts, and other parameters and conditions are exactly the same as those in example 1.
Example 5
This example differs from example 1 only in that the amount of polytetrafluoroethylene emulsion added in step (1) is 0.5 parts, and other parameters and conditions are exactly the same as those in example 1.
Example 6
This example differs from example 1 only in that the amount of polytetrafluoroethylene emulsion added in step (1) is 1.0 part, and other parameters and conditions are exactly the same as those in example 1.
Comparative example 1
This comparative example differs from example 1 only in that the amount of the superconducting carbon black added in step (1) is 0.08 parts, and other parameters and conditions are exactly the same as those in example 1.
Comparative example 2
This comparative example differs from example 1 only in that the amount of the superconducting carbon black added in step (1) is 0.6 parts, and other parameters and conditions are exactly the same as those in example 1.
Comparative example 3
This comparative example differs from example 1 only in that the amount of polytetrafluoroethylene emulsion added in step (1) is 0.4 parts, and other parameters and conditions are exactly the same as those in example 1.
Comparative example 4
This comparative example differs from example 1 only in that the amount of polytetrafluoroethylene emulsion added in step (1) was 1.2 parts, and other parameters and conditions were exactly the same as those in example 1.
Comparative example 5
This comparative example employed a conventional positive electrode having a carbon pack as shown in fig. 2. The specific manufacturing method comprises the following steps:
(1) the same procedure as in step (1) of example 1 was repeated.
(2) The same as the step (2) in example 1
(3) And (3) putting the dried powder in the step (2) into a 180 ℃ drying oven for drying for 6 hours, then heating the drying oven to 260 ℃, and continuously drying the powder for 20 minutes.
(4) And (4) uniformly stirring the materials baked in the step (3) for 3 minutes by using a stirrer.
(5) And (4) screening the stirred material in the step (4) to obtain anode particles with the particle size of 2-3 mm.
Comparative example 6
This comparative example provides a lithium thionyl chloride battery positive electrode containing a metal conductive agent, which is different from example 5 only in that 0.3 part of the metal conductive agent was further added in the mixing of acetylene black and superconducting carbon black in step (1), and other parameters and conditions were exactly the same as those in example 5.
And (3) performance testing:
carrying out liquid absorption test on the above examples 1-6 and comparative examples 1-6, assembling the positive electrode, the steel shell, the lithium belt, the glass fiber diaphragm and the cover assembly of the above examples 1-6 and comparative examples 1-6 on an automatic line to obtain a semi-finished battery, finally injecting electrolyte, sealing to obtain a battery finished product, and carrying out output electric quantity test on the battery finished product, wherein the battery model is ER14250, and the test results are shown in Table 1:
TABLE 1
| Injection amount/g | Amount of liquid absorbed by the charcoal bag/g | Imbibition rate/%) | Output electric quantity/Ah | |
| Example 1 | 3.2928 | 3.1683 | 96.22 | 1.11 |
| Example 2 | 3.3263 | 3.1676 | 95.23 | 1.11 |
| Example 3 | 3.3174 | 3.1887 | 96.12 | 1.03 |
| Example 4 | 3.2934 | 3.1323 | 95.11 | 1.05 |
| Example 5 | 3.2976 | 3.1146 | 94.45 | 1.00 |
| Example 6 | 3.3152 | 3.1869 | 93.13 | 1.02 |
| Comparative example 1 | 3.2910 | 2.2487 | 68.33 | 0.85 |
| Comparative example 2 | 3.2922 | 2.3082 | 70.11 | 0.90 |
| Comparative example 3 | 3.3168 | 2.3626 | 71.23 | 0.94 |
| Comparative example 4 | 3.3015 | 2.1902 | 66.34 | 0.95 |
| Comparative example 5 | 3.2917 | 2.1612 | 65.66 | 0.70 |
| Comparative example 6 | 3.2876 | 2.2067 | 67.12 | 0.75 |
As can be seen from table 1:
(1) the positive electrode plates prepared in examples 1 to 6 all have excellent properties of large liquid absorption capacity and large output capacity, wherein in examples 3 to 4, the addition amount of the superconducting carbon black is adjusted to 0.1 or 0.5 part, that is, when the addition amount is not within the preferable range of the invention, the discharge capacity of the battery is reduced, and the properties are reduced to a certain extent; examples 5-6 adjusting the amount of polytetrafluoroethylene solution added to 0.5 or 1.0 part, i.e., outside the preferred range of the present invention, also resulted in a decrease in the battery discharge capacity and a certain reduction in performance.
(2) Comparing example 1 with comparative examples 1-2, it can be seen that the superior performance of the present invention, which is high in liquid absorption rate and large in discharge capacity, can not be achieved when the content of the superconducting carbon black added in comparative examples 1-2 is too much or too little, and thus it can be shown that the superior performance, which is good in liquid absorption, can be better achieved by adjusting the content of the superconducting carbon black in the present invention;
(3) as can be seen by comparing example 1 with comparative examples 3 to 4, in comparative examples 3 to 4, the polytetrafluoroethylene emulsion is out of the range of the present invention, resulting in a low liquid absorption rate and a low discharge capacity;
(4) comparing the embodiment 1 with the comparative example 5, it can be seen that the liquid absorption rate of the anode provided by the invention is greatly improved by more than 30% compared with the liquid absorption rate of the traditional anode.
(5) Comparing example 1 with comparative example 6, it can be seen that the lithium thionyl chloride battery positive electrode of the present invention does not contain a metal conductive agent, reduces heat generated by a voltage difference formed by electrons transmitted through the metal conductive agent, and improves the output capacity of the battery.
The finished battery obtained by the positive electrode shown in example 1 and an ER34615 (type D) battery were subjected to a comparative performance test at a discharge temperature of 21 ℃ at a low current of 10mA and a cut-off voltage of 2.0V, and the test results are shown in fig. 4. As can be seen from fig. 4, the discharge capacity of the battery including the positive electrode of the lithium thionyl chloride battery according to the present invention was increased by 11% and the voltage was increased by 1.5% as compared to the ER34615(D type) battery.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The lithium thionyl chloride battery positive electrode material is characterized by comprising acetylene black, superconducting carbon black, absolute ethyl alcohol, deionized water and polytetrafluoroethylene emulsion;
the mass ratio of the acetylene black, the superconducting carbon black, the absolute ethyl alcohol, the deionized water and the polytetrafluoroethylene emulsion is 10 (0.1-0.5): 1.0-3.0): 15-25): 0.5-1.0.
2. The positive electrode material of a lithium thionyl chloride battery as claimed in claim 1, wherein the mass ratio of the acetylene black, the superconducting carbon black, the absolute ethyl alcohol, the deionized water and the polytetrafluoroethylene emulsion is 10 (0.2-0.5): 2-3): 20-25): 0.8-1.0;
preferably, the superconducting carbon black is any one or a combination of at least two of powdered N472, EC300JD or Vulcan XC-72, preferably Vulcan XC-72;
preferably, the particle size of the superconducting carbon black is 20-30 nm;
preferably, the polytetrafluoroethylene emulsion is an aqueous emulsion with the mass fraction of 50-70%, and preferably an aqueous emulsion with the mass fraction of 60%.
3. A positive electrode tab of a lithium thionyl chloride battery, wherein the positive electrode tab comprises the positive electrode material of the lithium thionyl chloride battery as claimed in claim 1 or 2.
4. The preparation method of the positive pole piece of the lithium thionyl chloride battery as claimed in claim 3, characterized by comprising the following steps:
(1) mixing acetylene black, superconducting carbon black, absolute ethyl alcohol, deionized water and polytetrafluoroethylene emulsion according to a ratio to obtain a paste material;
(2) and (2) drying, crushing, filtering, fiberizing, extruding and cutting the paste material obtained in the step (1) in sequence to obtain the lithium thionyl chloride battery positive pole piece.
5. The method according to claim 4, wherein the mixing of step (1) specifically comprises:
(a) mixing acetylene black and superconducting carbon black to obtain a mixture;
(b) wet mixing the mixture obtained in the step (a) by using absolute ethyl alcohol and deionized water to obtain a wet material;
(c) adding the polytetrafluoroethylene emulsion into the wet material obtained in the step (b), and continuously stirring to obtain a paste material.
6. The production method according to claim 4 or 5, wherein the mixing in the step (1) is performed using a high-speed stirrer;
preferably, the mixing speed in the step (a) is 20-30 r/min, preferably 25 r/min;
preferably, the mixing stirring time is 0.5-1.5 h, preferably 1 h;
preferably, the stirring speed of the wet mixing in the step (b) is 25-35 r/min, and preferably 30 r/min;
preferably, the stirring time of the wet mixing is 25-35 min, preferably 30 min;
preferably, the speed of continuously stirring after adding the polytetrafluoroethylene emulsion in the step (c) is 3-8 r/min, and preferably 5 r/min;
preferably, the time for continuing stirring is 8-12 min, and preferably 10 min.
7. The preparation method according to any one of claims 4 to 6, wherein the drying temperature of the paste material in the step (2) is 50 to 70 ℃;
preferably, the drying time of the paste material is 10-14 h, and preferably 12 h.
8. The method according to any one of claims 4 to 7, wherein the means for filtering of step (2) comprises a filtering screen;
preferably, the mesh number of the filtering screen is 150-250 meshes, and preferably 200 meshes;
preferably, the fiberization treatment in step (2) is carried out in an oven;
preferably, the temperature of the fiberization treatment is 250-350 ℃, and preferably 300 ℃;
preferably, the time of the fiberization treatment is 1.5-2.5 h, and preferably 2 h.
9. The method of any one of claims 4 to 8, comprising:
(1') mixing acetylene black and superconducting carbon black in a high-speed mixer with the mixing speed of 20-30 r/min for 0.5-1.5 h to obtain a mixture;
(2 ') carrying out wet mixing on the mixture obtained in the step (1') by using absolute ethyl alcohol and deionized water, wherein the stirring speed of the wet mixing is 25-35 r/min, and the stirring time is 25-35 min, so as to obtain a wet material;
(3 ') adding polytetrafluoroethylene emulsion into the wet material obtained in the step (2'), and continuously stirring for 8-12 min at a stirring speed of 3-8 r/min to obtain a paste material;
(4 ') drying the paste material obtained in the step (3') in a drying oven at the temperature of 50-70 ℃ for 10-14 h;
(5 ') putting the dried paste material in the step (4') into a crusher to be crushed and sieving the crushed paste material with a sieve of 150-250 meshes to obtain particles with uniform particle size;
(6 ') placing the filtered particles obtained in the step (5') into an oven at the temperature of 250-350 ℃ for fiberization for 1.5-2.5 h;
(7 ') placing the fibrillated particles obtained in the step (6') into a carbon bag forming machine, and carrying out extrusion forming to obtain a positive carbon bag;
(8 ') cutting the positive electrode carbon bag obtained in the step (7') by using a slitting knife to obtain the positive electrode piece of the lithium thionyl chloride battery.
10. A lithium thionyl chloride cell comprising the positive electrode tab of claim 3.
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Cited By (1)
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| CN116779767A (en) * | 2023-08-17 | 2023-09-19 | 蔚来电池科技(安徽)有限公司 | Electrode plate, preparation method thereof, secondary battery and device |
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Address after: 430000, No.1, Taichung Avenue, Gaoqiao Industrial Park, Wujiashan Economic Development Zone, Wuhan City, Hubei Province Applicant after: Wuhan Haocheng lithium Technology Co.,Ltd. Address before: 430000, No.1, Taichung Avenue, Gaoqiao Industrial Park, Wujiashan Economic Development Zone, Wuhan City, Hubei Province Applicant before: WUHAN HAOCHENG ENERGY RESOURCES TECHNOLOGY Co.,Ltd. |
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Application publication date: 20210205 |