CN115911252A - Magnesium/cuprous chloride seawater battery, positive electrode material and preparation method thereof - Google Patents
Magnesium/cuprous chloride seawater battery, positive electrode material and preparation method thereof Download PDFInfo
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- CN115911252A CN115911252A CN202211469243.0A CN202211469243A CN115911252A CN 115911252 A CN115911252 A CN 115911252A CN 202211469243 A CN202211469243 A CN 202211469243A CN 115911252 A CN115911252 A CN 115911252A
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- 229910021591 Copper(I) chloride Inorganic materials 0.000 title claims abstract description 64
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 title claims abstract description 64
- 229940045803 cuprous chloride Drugs 0.000 title claims abstract description 64
- 239000013535 sea water Substances 0.000 title claims abstract description 46
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 19
- 239000011777 magnesium Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910001629 magnesium chloride Inorganic materials 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 53
- 238000002844 melting Methods 0.000 claims abstract description 21
- 230000008018 melting Effects 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 17
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000155 melt Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 239000010406 cathode material Substances 0.000 claims description 9
- 238000005266 casting Methods 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000000498 cooling water Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 9
- 238000007789 sealing Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 238000010309 melting process Methods 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007723 die pressing method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a magnesium/cuprous chloride seawater battery, a positive electrode material and a preparation method thereof, and belongs to the technical field of seawater batteries. The preparation method comprises the following steps: mixing cuprous chloride powder and cuprous sulfide powder according to a ratio of 95-99: 1-5 to obtain electrode powder; placing the electrode powder in a melting device, sealing and heating to 450-520 ℃, and preserving heat for 2-4 h to obtain a molten mass; and pouring the molten mass onto a pair of rollers of a roller press provided with a current collector, cooling and crystallizing the molten mass through the pair of rollers, and embedding the current collector in the middle of crystals to prepare the strip-shaped electrode. The cuprous chloride powder and the cuprous sulfide powder are mixed, heated and melted, and then continuously poured to the roller press machine prefabricated with the current collector, so that the conductivity of the cuprous chloride anode is improved, the current collecting condition of the anode is improved, and the high-current discharge performance, particularly the initial-stage voltage, is improved.
Description
Technical Field
The invention belongs to the technical field of seawater batteries, and particularly relates to a magnesium/cuprous chloride seawater battery, a positive electrode material and a preparation method of the magnesium/cuprous chloride seawater battery.
Background
A magnesium/cuprous chloride (CuCl) seawater battery is prepared from seawater as electrolyte, cuprous chloride as main anode and magnesium alloy as negative electrode through filling seawater in the anode for discharging. The reaction of the cell is as follows:
negative electrode Mg → Mg 2+ +2e
Positive electrode CuCl + e → Cu + Cl –
Total reaction Mg +2CuCl → MgCl 2 +2Cu
The magnesium/cuprous chloride seawater battery as a disposable power battery has the following characteristics:
(1) The specific energy and the specific power are relatively high. The battery works in a non-sealing state and is in substance transfer with the outside;
(2) The structure is simple: the device can stably work after being immersed in seawater, and the galvanic pile has a laminated structure, simple structure and reliable performance;
(3) Safety: the combustion and explosion can not occur during the storage, transportation and use periods, and the safety is excellent;
(4) Long storage life: the storage is carried out in a dry state, and the self-discharge is avoided, so that the storage can be carried out for a long time;
(5) The cost is low: the cathode material is low in price and has cost advantage.
Generally, the battery positive electrode is produced by a melting ingot-free rolling method: and (3) preparing the molten cuprous chloride and the copper mesh into a strip-shaped positive electrode by using a roller press. The positive electrode of the battery produced in this manner has poor conductivity, and when used as a positive electrode, the battery has a long activation time and a low voltage.
In order to further increase the conductivity of the electrode, a conductive agent needs to be added. Graphite powder is commonly used, but the graphite material can generate oxidation reaction at about 400 ℃, and O physically adsorbed on the surface of the graphite material 2 Chemically reacting with graphite material to convert into CO, and further converting into CO 2 Eventually leaving the surface of the material and thus the conductivity of the electrode is not greatly enhanced by the addition of graphite powder.
In the prior art, metal powder such as platinum powder, gold powder, silver powder, aluminum powder, copper powder, nickel powder and the like is added into the anode material to increase the conductivity of the anode material, but the addition of the metal powder improves the performance of the magnesium/cuprous chloride seawater battery, and is not beneficial obviously. In addition, the commonly used preparation method of the cuprous chloride electrode is a pressing and sintering process, a copper net or a nickel net is used as a framework in the middle, the process is not suitable for manufacturing large-area power type electrodes, and the sheet type pressing and sintering method is low in production efficiency and is not suitable for large-scale production.
In view of the above, the invention is especially provided for further effectively improving the anode conductivity of the magnesium/cuprous chloride seawater battery.
Disclosure of Invention
The invention aims to provide a magnesium/cuprous chloride seawater battery, a positive electrode material and a preparation method thereof.
The invention is realized by the following technical scheme:
in a first aspect, the invention provides a preparation method of a cuprous chloride seawater battery positive electrode material, which comprises the following steps:
mixing cuprous chloride powder and cuprous sulfide powder according to a ratio of 95-99: 1-5 to obtain electrode powder;
placing the electrode powder in a melting device, sealing and heating to 450-520 ℃, and preserving heat for 2-4 h to obtain a molten mass;
and pouring the molten mass onto a pair of rollers of a roller press provided with a current collector, cooling and crystallizing the molten mass through the pair of rollers, and embedding the current collector in the middle of crystals to prepare the strip-shaped electrode.
Further, in a preferred embodiment of the present invention, in the cooling crystallization of the molten mass by the pair of rollers, the temperature of the cooling water for the rollers is 40 to 50 ℃.
Further, in a preferred embodiment of the present invention, before the casting the molten mass on the counter roll, the casting method further comprises: adjusting the gap between the rollers of the roller press to be 0.3-0.7 mm, thereby obtaining the strip-shaped electrode with the thickness of 0.3-0.7 mm.
Further, in a preferred embodiment of the present invention, the melt is poured onto the pair of rollers through a melt pouring diverter disposed above the rollers of the pair of rollers, and the temperature of the melt pouring diverter is 450 to 520 ℃ when the melt is poured.
Further, in the preferred embodiment of the present invention, the casting speed of the melt is to maintain the height of the liquid level at 5-10 cm; the rotating speed of the rollers of the pair rollers is 2-10 m/min.
Further, in a preferred embodiment of the present invention, the current collector includes at least one of a nickel mesh, a copper mesh, an aluminum mesh, and a nickel foam.
In a second aspect, the invention also provides a cuprous chloride seawater battery anode material, which is prepared by the preparation method.
Furthermore, in a preferred embodiment of the invention, the cuprous chloride seawater battery positive electrode material is a strip electrode, and the length of the strip electrode is 100-300 m; the width of the strip electrode was 500mm.
In a third aspect, the magnesium/cuprous chloride seawater battery adopts the cathode material of the cuprous chloride seawater battery as a cathode.
Furthermore, in the preferred embodiment of the invention, the current density of the magnesium/cuprous chloride seawater battery is more than or equal to 180mA/cm 2 。
Compared with the prior art, the invention has the following technical effects:
the cuprous chloride powder and the cuprous sulfide powder are mixed, heated and melted, then continuously poured into a roller press with a prefabricated current collector, and a continuous electrode belt is poured out through a roller cooling melt of the roller press, so that the strip-shaped cuprous chloride seawater battery anode material is obtained. Compared with materials such as graphite, the cuprous sulfide can better resist the melting temperature, and the cuprous sulfide exists in the cuprous chloride anode all the time and does not participate in chemical reaction. Meanwhile, cuprous sulfide is a semiconductor, which is beneficial to improving the conductivity of the cuprous chloride anode, improving the current collection condition of the anode and improving the large-current discharge performance, especially the initial-stage voltage.
Meanwhile, the invention also has the following advantages:
1) The method of melting and continuous pouring is adopted, the production efficiency is high, and the method is suitable for batch production.
2) The roller press is used for rolling and forming, and the thickness is uniform and the precision is high.
3) The melt is cooled and crystallized by a roller of a roller press, and the electrode belt has uniform texture.
4) By adjusting the gap between the rollers of the roller press, thin electrodes with different thicknesses can be produced.
5) The width of the electrode belt is directly adjusted by adjusting the length of the roller.
Drawings
FIG. 1 is a schematic process flow diagram of example 1 of the present invention;
FIG. 2 is a schematic structural view of a roll press apparatus used in example 1 of the present invention;
fig. 3 is a comparative curve of electrical property test in the experimental example of the present invention.
Some of the drawings are illustrated below:
a melting furnace 1; a melt 2; pouring the shunt 3; a pair roller 4; a copper mesh reel 5; a copper mesh belt 6; an electrode belt 7; a net collecting roller 8.
Detailed Description
Embodiments of the present invention will be described in detail with reference to the following examples, but those skilled in the art will understand that the following examples are merely illustrative of the present invention and should not be construed as limiting the scope of the present invention, and that the specific conditions not specified in the examples are carried out according to conventional conditions or conditions suggested by the manufacturer, and that the reagents or equipment used are not specified by the manufacturer, and are all conventional products available through commercial purchase.
The invention conception of the invention is as follows: the method comprises the steps of melting the powder at high temperature, and then continuously casting, crystallizing and rolling the melt through a rolling machine to manufacture a continuous electrode belt. The conventional die pressing sintering process is suitable for manufacturing small-batch electrodes, has the phenomenon of inconsistent thickness, and is low in yield particularly when large-area electrodes are manufactured.
The technical scheme of the invention is as follows:
the preparation method of the cuprous chloride seawater battery cathode material comprises the following steps:
step S1, mixing cuprous chloride powder and cuprous sulfide powder according to the ratio of 95-99 to 1-5 to obtain electrode powder;
in the step, cuprous chloride powder is used as a main material of the positive electrode, cuprous sulfide powder is used as an active additive, and Cu is added 2 S is a semiconductor and contributes to the improvement of the conductivity of the cuprous chloride positive electrode. The mass ratio of the cuprous chloride powder to the cuprous sulfide powder in the electrode powder in the step is 95-99, namely the addition amount of the cuprous sulfide is 1-5%, preferably 2-4%. The inventor researches and discovers that when the addition amount is less than 1%, the climbing time of the battery voltage is obviously prolonged, and the requirement of quick activation cannot be met; when the additive amount is more than 5%, the increase of the voltage rising time of the battery is not large, whereas excessive additives affect the capacity of the battery.
Step S2: placing the electrode powder in a melting device, sealing and heating to 450-520 ℃, and preserving heat for 2-4 h to obtain a molten mass;
in this step, the purpose of sealing and heating is mainly to make the electrode powder in a completely molten state, which is helpful for the subsequent casting step. In the specific operation process, the electrode powder is poured into a melting furnace to be evenly spread, and a sealing cover is covered to heat. The heating temperature and time can be selected according to experimental requirements, and preferably, the heating temperature is 450-520 ℃ (more preferably 470-500 ℃); the holding time is 2 to 4 hours (more preferably 2.5 to 3.5 hours).
And step S3: and pouring the molten mass onto a pair of rollers of a roller press provided with a current collector, cooling and crystallizing the molten mass through the pair of rollers, and embedding the current collector in the middle of crystals to prepare the strip-shaped electrode.
Compared with the traditional chip pressing and sintering method, the melting continuous casting method provided by the invention has high production efficiency and is more suitable for large-scale production.
Further, before the molten mass is poured onto the pair of rollers, the method further comprises the following steps: the roller gap of the roller press is adjusted to be 0.3-0.7 mm. The thickness of the manufactured strip-shaped electrode can be controlled by adjusting the gap between the rollers of the roller press. Generally, the thickness of the strip electrode is generally between 0.3 and 0.7mm, which is more suitable for high-power discharge, and the electrode active material utilization rate is highest in this range. More preferably, the thickness of the strip-shaped electrode is 0.5mm ± 0.05mm.
Furthermore, in the process of cooling and crystallizing the melt by the pair of rollers, the temperature of roller cooling water of the pair of rollers is 40-50 ℃, preferably 42-47 ℃) and proper cooling capacity of the rollers needs to be maintained in the pouring process, the cooling water with the temperature is used for cooling the rollers, the consistency of the crystallization state of the electrode belt is maintained, and if the cooling temperature is too low, excessive segregation phenomenon is easily caused.
Further, the melt is poured onto the roller pair through the melt pouring diverter, the melt pouring diverter is arranged above the roller pair, when the melt is poured, the temperature of the melt pouring diverter is 450-520 ℃, and at the temperature, the melt is good in mobility and not prone to solidification and blockage when the melt passes through the melt pouring diverter, so that the continuity of electrode strip pouring is guaranteed.
Further, the pouring speed of the molten mass is 5-10 cm for keeping the liquid level height; the roller speed of the pair rollers is 2-10 m/min.
In the casting process, the speed of a roller needs to be adjusted according to the surface state of an electrode belt pressed by the roller: 1) In the rolling process, the state of an electrode belt pressed by a roller needs to be observed, if liquid drops are condensed on the surface of the electrode belt, the cooling of the melt is insufficient, the rotating speed of a roller needs to be reduced, and the cooling time of the melt on the roller is prolonged; 2) If the surface of the electrode belt extruded by the roller is too bright, the melt is excessively cooled, the rotating speed of the roller needs to be increased, and the cooling time of the melt on the roller is shortened.
The melt is made to have certain height on the roller by regulating the pouring speed of the melt and the rotation speed of the roller, so as to form a continuous strip electrode. More preferably, the length of the strip-shaped electrode is 100 to 300m; the width of the strip electrode was 500mm.
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Example 1
The embodiment provides a cuprous chloride seawater battery cathode material, the preparation process flow of which is shown in fig. 1, the used roller press equipment is shown in fig. 2, and the roller press comprises: the device comprises a melting furnace 1, a molten mass 2, a pouring shunt 3, a pair of roller wheels 4, a current collector reel 5, a current collector mesh belt 6, an electrode belt 7 and a net collecting roller 8.
The preparation method of the cuprous chloride seawater battery positive electrode material comprises the following steps:
1) The main material for the positive electrode is CuCl powder and Cu 2 S powder as additive, mixing CuCl powder with Cu 2 And (3) putting the S powder into a mixer according to the mass ratio of 99.
2) The electrode material is poured into the melting furnace 1 and evenly spread, the inner wall of the melting furnace generally adopts copper alloy, harmful substances such as iron ions and the like are prevented from being introduced in the melting process, and a sealing cover is covered.
3) Heating the melting furnace to 450-470 ℃, and preserving heat for 2-2.5 h according to the input amount of the electrode powder to fully melt the electrode powder.
4) The gap between the double-roller 4 of the roller press is adjusted to the thickness of the electrode strip to be adjusted, and the roller cooling water is started and the temperature is adjusted to 40-43 ℃.
5) And (3) placing a current collector reel 5 (a copper wire reel in the embodiment) on a net placing frame, connecting the copper wire to a net collecting roller 8 through a roller gap, and leveling.
6) The melt pouring splitter 3 is placed above the rolls and heated to 450-470 ℃.
7) The melted body 2 of the electrode powder slowly and uniformly flows into the pouring splitter 3, and the pouring splitter 3 uniformly pours the melted body between the roller wheels 4 of the roller press.
8) And opening the roller press and adjusting the rollers to rotate in the direction of the rollers, and cooling and crystallizing the melt through the rollers to embed the copper mesh in the middle of the crystal.
9) And adjusting the gap of the roller to be 0.3mm in the pouring process.
Through pouring, the thickness of the finally obtained cuprous chloride seawater battery anode strip is 0.3mm +/-0.05 mm, the length can exceed 110m, and the width can reach 500mm.
Example 2
The embodiment provides a cuprous chloride seawater battery cathode material, and a preparation method thereof comprises the following steps:
1) The main material of the anode is CuCl powder and Cu 2 S powder as additive, mixing CuCl powder with Cu 2 And (3) putting the S powder into a mixer according to the mass ratio of 95.
2) The electrode material is poured into the melting furnace 1 and evenly spread, the inner wall of the melting furnace generally adopts copper alloy, harmful substances such as iron ions and the like are prevented from being introduced in the melting process, and a sealing cover is covered.
3) Heating the melting furnace to 500-520 ℃, and preserving heat for 3-3.5 hours according to the input amount of the electrode powder to fully melt the electrode powder.
4) The gap between the double-roller 4 of the roller press is adjusted to the thickness of the electrode strip to be adjusted, and the roller cooling water is started and the temperature is adjusted to be 48-50 ℃.
5) The current collector reel 5 (nickel screen reel in the embodiment) is placed on the screen placing frame, and the nickel screen is connected to the screen receiving roller 8 through the gap of the rollers and is pulled to be flat.
6) The melt pouring splitter 3 is placed above the rolls and heated to 500-520 ℃.
7) The melted body 2 of the electrode powder slowly and uniformly flows into the pouring splitter 3, and the pouring splitter 3 uniformly pours the melted body between the roller wheels 4 of the roller press.
8) And opening the roller press and adjusting the rollers to rotate in the direction of the rollers, cooling and crystallizing the melt through the rollers, and embedding the nickel screen in the middle of the crystal.
9) And adjusting the gap of the roller to be 0.7mm in the casting process.
Through pouring, the thickness of the finally obtained cuprous chloride seawater battery anode strip is 0.7mm +/-0.05 mm, the length can exceed 100m, and the width can reach 520mm.
Example 3
The embodiment provides a cuprous chloride seawater battery cathode material, and a preparation method thereof comprises the following steps:
1) The main material for the positive electrode is CuCl powder and Cu 2 S powder as additive, mixing CuCl powder with Cu 2 And (3) putting the S powder into a mixer according to the mass ratio of 97.
2) The electrode material is poured into the melting furnace 1 and evenly spread, the inner wall of the melting furnace generally adopts copper alloy, harmful substances such as iron ions and the like are prevented from being introduced in the melting process, and a sealing cover is covered.
3) And heating the melting furnace to 470-480 ℃, and preserving heat for 2.5-3.5 h according to the input amount of the electrode powder to fully melt the electrode powder.
4) The gap between the double-roller 4 of the roller press is adjusted to the thickness of the electrode strip to be adjusted, and the roller cooling water is started and the temperature is adjusted to 44-46 ℃.
5) The current collector reel 5 (copper wire reel in the embodiment) is placed on the net placing frame, and the copper wire is connected to the net collecting roller 8 through the gap of the rollers and is pulled to be flat.
6) The melt pouring splitter 3 is placed above the roller and heated to 470-480 ℃.
7) The melted body 2 of the electrode powder slowly and uniformly flows into the pouring splitter 3, and the pouring splitter 3 uniformly pours the melted body between the roller wheels 4 of the roller press.
8) And opening the roller press and adjusting the rollers to rotate in the direction of the rollers, and cooling and crystallizing the melt through the rollers to embed the copper mesh in the middle of the crystal.
9) And adjusting the gap of the roller to be 0.5mm in the pouring process.
Through pouring, the thickness of the finally obtained cuprous chloride seawater battery anode strip is 0.5mm +/-0.05 mm, the length can exceed 130m, and the width can reach 550mm.
Comparative example 1
The comparative example provides a cuprous chloride seawater battery cathode material, the preparation steps of which are basically the same as those in example 3, except that: the material for the positive electrode is CuCl powder without adding Cu 2 And (4) S powder.
In order to illustrate the advantageous effects of the positive electrode materials for batteries provided in example 3 of the present invention and comparative examples 1 to 2, the following experiments were performed:
1. the experimental method comprises the following steps:
the electrode strip prepared by the method is processed to be made into a positive electrode, the magnesium alloy plate is processed to be used as a negative electrode, the middle part of the electrode strip is separated by nonmetal particles with the interval of about 8mm, the diameter of the nonmetal particles is about phi 0.8mm, the height of the nonmetal particles is about 0.5mm, and the electrode strip is compressed to form a single battery. Then, a flowing 3.3% aqueous solution of sodium chloride (simulated seawater) was introduced thereinto at 180mA/cm 2 The discharge test was performed.
2. The experimental results are as follows:
as shown in fig. 3, the average voltage was increased from 1.198V before addition (i.e., comparative example 1) to 1.274V after addition (i.e., example 3). Thus, cu was added 2 After S, the conductivity of the positive electrode material is enhanced. The time for the voltage to climb to 1.2V was increased from 54s before addition (i.e., comparative example 1) to 5.6s after addition (i.e., comparative example 1). Thus, cu was added 2 After S, the current collecting condition of the positive electrode is improved, and the large-current discharge performance, particularly the initial-stage voltage, is improved.
Finally, it should be noted that: the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a cuprous chloride seawater battery positive electrode material is characterized by comprising the following steps:
mixing cuprous chloride powder and cuprous sulfide powder according to a ratio of 95-99: 1-5 to obtain electrode powder;
the electrode powder is placed in a melting device to be sealed and heated to 450-520 ℃, and the temperature is kept for 2-4 hours to obtain a molten mass;
and pouring the molten mass onto a pair of rollers of a roller press provided with a current collector, cooling and crystallizing the molten mass through the pair of rollers, and embedding the current collector in the middle of crystals to prepare the strip-shaped electrode.
2. A method for preparing a cuprous chloride seawater battery positive electrode material according to claim 1, wherein the temperature of roller cooling water of said roller is 40-50 ℃ during the cooling crystallization of said molten mass by said roller.
3. A method for preparing a cuprous chloride seawater battery positive electrode material according to claim 1, wherein before pouring said molten mass onto said pair of rollers, further comprising: adjusting the gap between the rollers of the roller press to be 0.3-0.7 mm, thereby obtaining the strip-shaped electrode with the thickness of 0.3-0.7 mm.
4. The method for preparing a cuprous chloride seawater battery positive electrode material according to claim 1, wherein the melt is poured onto the counter roller by a melt pouring diverter placed above the roller of the counter roller, and the temperature of the melt pouring diverter is 450-520 ℃ when the melt is poured.
5. The method for preparing the cuprous chloride seawater battery positive electrode material according to claim 4, wherein the casting speed of the molten mass is to keep the liquid level height at 5-10 cm; the roller speed of the pair rollers is 2-10 m/min.
6. The method for preparing a cuprous chloride seawater battery positive electrode material according to claim 1, wherein said current collector comprises at least one of nickel mesh, copper mesh, aluminum mesh and nickel foam.
7. A cuprous chloride seawater battery cathode material, characterized in that the cuprous chloride seawater battery cathode material is prepared by the preparation method of any one of claims 1 to 6.
8. The cuprous chloride seawater battery positive electrode material according to claim 7, wherein the cuprous chloride seawater battery positive electrode material is a strip electrode, and the length of the strip electrode is 100-300 m; the width of the strip-shaped electrode is 500mm.
9. A magnesium/cuprous chloride seawater battery, characterized in that the cuprous chloride seawater battery positive electrode material according to any one of claims 7 or 8 is used as a positive electrode.
10. The magnesium/cuprous chloride seawater battery of claim 9, wherein the current density of said magnesium/cuprous chloride seawater battery is greater than or equal to 180mA/cm 2 。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB726826A (en) * | 1952-12-23 | 1955-03-23 | Mcmurdo Instr Company Ltd | Improvements in and relating to the manufacture of galvanic batteries |
| CN104495908A (en) * | 2014-12-31 | 2015-04-08 | 湖南稀土金属材料研究院 | Preparation method of cuprous sulfide powder, and cuprous sulfide powder |
| CN109244359A (en) * | 2018-11-06 | 2019-01-18 | 南京径祥新材料科技有限公司 | A kind of high capacity Magnesium sea water battery stannous chloride anode pole piece moulding process and gained battery |
| CN111822662A (en) * | 2019-04-17 | 2020-10-27 | 青岛九环新越新能源科技股份有限公司 | Continuous production equipment for composite metal strip |
-
2022
- 2022-11-22 CN CN202211469243.0A patent/CN115911252A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB726826A (en) * | 1952-12-23 | 1955-03-23 | Mcmurdo Instr Company Ltd | Improvements in and relating to the manufacture of galvanic batteries |
| CN104495908A (en) * | 2014-12-31 | 2015-04-08 | 湖南稀土金属材料研究院 | Preparation method of cuprous sulfide powder, and cuprous sulfide powder |
| CN109244359A (en) * | 2018-11-06 | 2019-01-18 | 南京径祥新材料科技有限公司 | A kind of high capacity Magnesium sea water battery stannous chloride anode pole piece moulding process and gained battery |
| CN111822662A (en) * | 2019-04-17 | 2020-10-27 | 青岛九环新越新能源科技股份有限公司 | Continuous production equipment for composite metal strip |
Non-Patent Citations (1)
| Title |
|---|
| 王宇轩等: "海水电池氯化亚铜电极含硫添加剂", 《电源技术》, 20 April 2007 (2007-04-20), pages 322 * |
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