CN114843117A - Metal sulfide energy storage electrode and preparation method and application thereof - Google Patents
Metal sulfide energy storage electrode and preparation method and application thereof Download PDFInfo
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- 229910052976 metal sulfide Inorganic materials 0.000 title claims abstract description 64
- 238000004146 energy storage Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 239000011248 coating agent Substances 0.000 claims abstract description 33
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 30
- 229910016507 CuCo Inorganic materials 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 229910016897 MnNi Inorganic materials 0.000 claims abstract description 17
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 17
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 16
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000011343 solid material Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000000853 adhesive Substances 0.000 claims abstract description 10
- 230000001070 adhesive effect Effects 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 210000000352 storage cell Anatomy 0.000 claims description 3
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000003487 electrochemical reaction Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000003860 storage Methods 0.000 description 5
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- 239000003990 capacitor Substances 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
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- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 238000004993 emission spectroscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention relates to the technical field of electrochemical energy storage materials, and discloses a metal sulfide energy storage electrode and a preparation method and application thereof. The method comprises the following steps: (1) mixing CuCo 2 S 4 、NiCo 2 S 4 、MnNi 2 S 4 、ZrS 2 Carrying out first contact mixing to obtain a first mixture; (2) in the presence of a solvent I, carrying out a first contact reaction on the first mixture and sodium sulfide, and sequentially carrying out first cleaning and first drying on a product obtained after the first contact reaction to obtain a first solid material; (3) in the presence of a solvent II, heating the first solid material to obtain a metal sulfide; (4) and carrying out second contact mixing on the metal sulfide and the conductive adhesive to obtain a coating liquid, and coating the coating liquid on the surface of the metal current collector. The invention providesThe method can prepare the metal sulfide energy storage electrode with high conductivity, good cycle performance and long service life.
Description
Technical Field
The invention relates to the technical field of electrochemical energy storage materials, in particular to a metal sulfide energy storage electrode and a preparation method and application thereof.
Background
With the development of society and the increase of population, the shortage of resources and energy sources becomes an urgent problem to be solved. Therefore, development of new energy sources and new energy storage technologies is imperative.
Energy storage devices such as super capacitors have attracted extensive attention due to the advantages of high charging speed, high power density, long service life, easy maintenance, environmental friendliness and the like, and are generally applied to a plurality of fields such as electric vehicles and storage batteries. How to enhance the conductivity of the super capacitor and improve the transmission rate of electrons in the electrochemical reaction process becomes a key research object for scholars at home and abroad.
The electrode material has a great influence on the conductivity of energy storage elements such as a super capacitor. However, the existing energy storage element has the problems of low electrode conductivity, poor cycle performance, low electrochemical reaction efficiency and the like, and the wide application of the energy storage battery is restricted.
Disclosure of Invention
The invention aims to solve the problems of low electrode conductivity, poor cycle performance and low electrochemical reaction efficiency in the prior art.
In order to achieve the above object, a first aspect of the present invention provides a method of producing a metal sulfide energy storage electrode, the method comprising:
(1) the molar ratio of the used amount is 1: 1-1.8: 1-1.8: 1-1.8 CuCo 2 S 4 、NiCo 2 S 4 、MnNi 2 S 4 、ZrS 2 Carrying out first contact mixing to obtain a first mixture;
(2) in the presence of a solvent I, carrying out a first contact reaction on the first mixture and sodium sulfide, and sequentially carrying out first cleaning and first drying on a product obtained after the first contact reaction to obtain a first solid material;
(3) in the presence of a solvent II, heating the first solid material to obtain a metal sulfide;
(4) carrying out second contact mixing on the metal sulfide and the conductive adhesive to obtain a coating liquid, and coating the coating liquid on the surface of the metal current collector; wherein the coating thickness of the coating liquid is 0.1-2 mm; at least two round holes are arranged on the metal current collector, and the surface area of the round holes accounts for 10-30% of the total surface area of the metal current collector.
In a second aspect, the invention provides a metal sulphide energy storage electrode produced by the method of the first aspect.
A third aspect of the invention provides the use of a metal sulphide energy storage electrode as described in the second aspect in an energy storage cell.
Compared with the electrode material in the prior art, the metal sulfide energy storage electrode provided by the invention has the characteristics of high conductivity, good cycle performance and long service life, and also has the advantages of high electrochemical reaction efficiency and high charging speed.
Drawings
Fig. 1 is a schematic view of the structure of a metal current collector in example 1 provided by the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
It should be noted that, in various aspects of the present invention, the present invention is described only once in one aspect thereof without repeated description with respect to the same components in the aspects, and those skilled in the art should not be construed as limiting the present invention.
In the present invention, unless otherwise specified, the room temperature or the room temperature both represent 25. + -. 2 ℃.
As previously mentioned, a first aspect of the invention provides a method of making a metal sulphide energy storage electrode, the method comprising:
(1) the molar ratio of the used amount is 1: 1-1.8: 1-1.8: 1-1.8 CuCo 2 S 4 、NiCo 2 S 4 、MnNi 2 S 4 、ZrS 2 Carrying out first contact mixing to obtain a first mixture;
(2) in the presence of a solvent I, carrying out a first contact reaction on the first mixture and sodium sulfide, and sequentially carrying out first cleaning and first drying on a product obtained after the first contact reaction to obtain a first solid material;
(3) in the presence of a solvent II, heating the first solid material to obtain a metal sulfide;
(4) carrying out second contact mixing on the metal sulfide and the conductive adhesive to obtain a coating liquid, and coating the coating liquid on the surface of the metal current collector; wherein the coating thickness of the coating liquid is 0.1-2 mm; at least two round holes are arranged on the metal current collector, and the surface area of the round holes accounts for 10-30% of the total surface area of the metal current collector.
The material of the metal current collector is not particularly required in the present invention, and a metal current collector known in the art may be used, and illustratively, the metal current collector in the present invention may be composed of at least one metal material of Cu, Li, Fe, and Mn.
The present invention does not particularly require the diameter of the circular holes on the metal current collector, and illustratively, the average diameter of the circular holes is 1 to 5 mm.
In the present invention, after the coating solution is coated on the surface of the metal current collector, the metal sulfide in the coating solution is electrochemically reacted on the surface of the metal current collector, and the chemical reaction formula is, for example, as shown in formula (1):
in the formula (1), A and B are different, A, B are respectively and independently selected from at least one of Mn, Co, Ni, Zr and Cu, and S represents sulfur.
Preferably, in step (1), the CuCo is 2 S 4 The NiCo 2 S 4 The MnNi 2 S 4 And said ZrS 2 The molar ratio of the used amount of the compound is 1: 1-1.5: 1.4-1.8: 1-1.5. The inventors have found that with this preferred embodiment, a metal sulphide energy storage electrode with higher electrochemical reaction efficiency can be obtained.
Preferably, in step (4), the surface area of the circular holes accounts for 20 to 30% of the total surface area of the metal current collector. The inventors have found that with this preferred embodiment, a metal sulphide energy storage electrode with higher conductivity can be obtained.
Preferably, in the step (4), the metal sulfide is coated to a thickness of 0.5 to 1.5 mm.
Preferably, in step (1), the conditions of the first contact mixing include at least: the temperature is 20-40 deg.C, the time is 10-60min, and the stirring speed is 40-80 rpm.
Preferably, in the step (2), the weight ratio of the first mixture to the sodium sulfide is 1: 1-3.
Preferably, in step (2), the weight ratio of the total weight of the first mixture and the sodium sulfide to the solvent I is 1: 4-6.
Preferably, in step (2), the conditions of the first contact reaction include at least: the temperature is 150 ℃ and 300 ℃, and the time is 3-5 h.
Preferably, in the step (2), the operation step of the first cleaning includes: and (3) washing the products obtained after the first contact reaction respectively for 3-5 times by adopting water and ethanol.
Preferably, in step (2), the conditions of the first drying include at least: the temperature is 60-100 ℃ and the time is 1-3 h.
Preferably, in step (3), the conditions of the heat treatment include at least: the temperature is 200 ℃ and 280 ℃, and the time is 5-10 h.
Preferably, in the step (3), the solvent II is used in an amount of 5 to 20g relative to 1g of the first solid material.
Preferably, in the step (4), the mass ratio of the metal sulfide to the conductive adhesive is 3-5: 1.
preferably, in step (4), the conditions of the second contact mixing include at least: the temperature is 20-40 deg.C, the time is 10-60min, and the stirring speed is 40-80 rpm.
Preferably, both the solvent I and the solvent II are water.
As previously mentioned, a second aspect of the invention provides a metal sulphide energy storage electrode produced by the method of the first aspect.
As previously mentioned, a third aspect of the invention provides the use of a metal sulphide energy storage electrode as described in the second aspect in an energy storage cell.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available unless otherwise specified.
CuCo 2 S 4 : prepared by the method provided by embodiment 1 in CN 106783233A;
NiCo 2 S 4 : prepared by the method provided by the embodiment 1 in CN 104201010A;
MnNi 2 S 4 : by using Mn 2+ Doped NiS
(MnxNi1-xS: x ═ 0.0,0.3and0.5) Nanocrystals: structures, morphology, Opto-mag networking and photonic Properties, except that the raw materials were in different amounts;
ZrS 2 : purchased from tezhou megana new energy limited;
conductive adhesive: the brand is Letuo 8801, purchased from Auja tuo electronic technology Limited, Shenzhen;
in the following examples, all metal current collectors were purchased from revo electric limited, mn and consisted essentially of 95.6 wt% Fe, with the balance being Li.
Metal current collector-1: as shown in fig. 1, each row is provided with 8 circular holes at intervals of 5mm, and each row is provided with 6 circular holes, and the interval between two adjacent rows is 5mm and is provided with 48 circular holes, and the surface area of the circular holes (with the average diameter of 1mm) accounts for 20% of the total surface area of the metal current collector;
metal current collector-2: the manner of making the round holes is similar to that of the metal current collector-1, except that: the average diameter of the circular holes is 1.5mm, so that the surface area of the circular holes accounts for 30% of the total surface area of the metal current collector;
metal current collector-3: the manner of making the round holes is similar to that of the metal current collector-1, except that: the average diameter of the circular holes is 0.5mm, so that the surface area of the circular holes accounts for 10% of the total surface area of the metal current collector;
metal current collector-4: no round hole is formed;
in the following examples, inductively coupled plasma emission spectrometry (ICP-OES) was used to detect the contents of Cu, Co, Ni, Mn, and Zr elements in the metal sulfide, respectively;
sodium sulfide is the analytically pure reagent in the following examples.
Example 1
The present embodiment provides a method of making a metal sulfide energy storage electrode, the method comprising the steps of:
(1) at room temperature, adding CuCo 2 S 4 、NiCo 2 S 4 、MnNi 2 S 4 、ZrS 2 Stirring at 60rpm for 40min to obtain a first mixture;
wherein the CuCo 2 S 4 The NiCo 2 S 4 The MnNi 2 S 4 And said ZrS 2 The molar ratio of the used amount of the compound is 1: 1.5: 1.7: 1.4 and CuCo 2 S 4 The dosage of the medicine is 410 g;
(2) carrying out a first contact reaction on the first mixture, sodium sulfide and water, respectively washing a product obtained after the first contact reaction for 3 times by using water and ethanol, and then drying the washed product at 60 ℃ for 2h to obtain a first solid material;
wherein the weight ratio of the first mixture to the sodium sulfide is 1: 1;
the weight ratio of the total weight of the first mixture and the sodium sulfide to the water is 1: 5;
the conditions of the first contact reaction include at least: the temperature is 150 ℃, and the time is 5 h;
(3) mixing the first solid material with water according to a solid-liquid weight ratio of 1:10, and then carrying out heating treatment to obtain a metal sulfide;
wherein the conditions of the heat treatment are as follows: the temperature is 200 ℃, and the time is 10 hours;
in the metal sulfide, the content molar ratio of Cu element, Co element, Ni element, Mn element and Zr element is 1: 4.8: 4.8: 1.7: 1.4;
(4) at room temperature, mixing the metal sulfide and the conductive adhesive according to a weight ratio of 5: 1 is stirred at 60rpm for 40min to obtain a coating solution, and the coating solution is uniformly coated on the surface of a metal current collector-1 with the coating thickness of 0.5mm to obtain a metal sulfide energy storage electrode S1.
Example 2
The present embodiment provides a method of making a metal sulfide energy storage electrode, the method comprising the steps of:
(1) at room temperature, adding CuCo 2 S 4 、NiCo 2 S 4 、MnNi 2 S 4 、ZrS 2 Stirring at 80rpm for 30min to obtain a first mixture;
wherein the CuCo 2 S 4 The NiCo 2 S 4 The MnNi 2 S 4 And said ZrS 2 The molar ratio of the used amount of the components is 1.4: 1.7: 2.0: 1.7 and CuCo 2 S 4 The dosage of the medicine is 574 g;
(2) carrying out a first contact reaction on the first mixture, sodium sulfide and water, respectively washing a product obtained after the first contact reaction for 3 times by using water and ethanol, and then drying the washed product at 80 ℃ for 1.5h to obtain a first solid material;
wherein the weight ratio of the first mixture to the sodium sulfide is 1: 3;
the weight ratio of the total weight of the first mixture and the sodium sulfide to the water is 1: 5;
the conditions of the first contact reaction include at least: the temperature is 150 ℃, and the time is 5 h;
(3) mixing the first solid material with water according to a solid-liquid weight ratio of 1:10, and then carrying out heating treatment to obtain a metal sulfide;
wherein the conditions of the heat treatment are as follows: the temperature is 200 ℃, and the time is 10 hours;
in the metal sulfide, the content molar ratio of Cu element, Co element, Ni element, Mn element and Zr element is 1.4: 6.2: 5.7: 2.0: 1.6;
(4) at room temperature, mixing the metal sulfide and the conductive adhesive according to a weight ratio of 5: 1 at 80rpm for 30min to obtain a coating solution, and uniformly coating the coating solution on the surface of a metal current collector-1 to obtain a metal sulfide energy storage electrode S2, wherein the coating thickness is 1.5 mm.
Example 3
The present embodiment provides a method of making a metal sulfide energy storage electrode, the method comprising the steps of:
(1) at room temperature, adding CuCo 2 S 4 、NiCo 2 S 4 、MnNi 2 S 4 、ZrS 2 Stirring at 50rpm for 40min to obtain a first mixture;
wherein the CuCo 2 S 4 The NiCo 2 S 4 The MnNi 2 S 4 And said ZrS 2 The molar ratio of the used amount of the components is 1.2: 1.8: 1.9: 1.7 and CuCo 2 S 4 In an amount of 492 g;
(2) carrying out a first contact reaction on the first mixture, sodium sulfide and water, respectively washing a product obtained after the first contact reaction for 3 times by using water and ethanol, and then drying the washed product at 100 ℃ for 1h to obtain a first solid material;
wherein the weight ratio of the first mixture to the sodium sulfide is 1: 2;
the weight ratio of the total weight of the first mixture and the sodium sulfide to the water is 1: 5;
the conditions of the first contact reaction include at least: the temperature is 150 ℃, and the time is 5 h;
(3) mixing the first solid material with water according to a solid-liquid weight ratio of 1:10, and then carrying out heating treatment to obtain a metal sulfide;
wherein the conditions of the heat treatment are as follows: the temperature is 200 ℃, and the time is 10 hours;
in the metal sulfide, the content molar ratio of Cu element, Co element, Ni element, Mn element and Zr element is 1.1: 6.0: 5.6: 1.9: 1.7;
(4) at room temperature, mixing the metal sulfide and the conductive adhesive according to a weight ratio of 5: 1 at 50rpm for 40min to obtain a coating solution, and uniformly coating the coating solution on the surface of a metal current collector-2 to obtain a metal sulfide energy storage electrode S3, wherein the coating thickness is 1.5 mm.
Example 4
A metal sulfide energy storage electrode was prepared according to the method of example 1, except that, in step (1), the CuCo was used 2 S 4 The NiCo 2 S 4 The MnNi 2 S 4 And said ZrS 2 The molar ratio of the used amount of the compound is 1: 1.8: 1.7: 1.4 and CuCo 2 S 4 The amount of (B) was 410 g.
Resulting in a metal sulfide storage electrode S4.
Example 5
A metal sulfide energy storage electrode was prepared according to the method of example 1, except that, in step (1), the CuCo was used 2 S 4 The NiCo 2 S 4 The MnNi 2 S 4 And said ZrS 2 The molar ratio of the used amount of the compound is 1: 1.5: 1: 1.4 and CuCo 2 S 4 The amount of (B) was 410 g.
Resulting in a metal sulfide storage electrode S5.
Example 6
A metal sulfide energy storage electrode was prepared according to the method of example 1, except that in step (4), metal current collector-1 was replaced with metal current collector-3.
A metal sulfide storage electrode S6 is obtained.
Example 7
A metal sulphide energy storage electrode was prepared as in example 1, except that in step (4) the metal sulphide was applied at a thickness of 2 mm.
A metal sulfide storage electrode S7 is obtained.
Comparative example 1
This comparative example A metal sulfide energy storage electrode was prepared according to the method of example 1, except that in step (1), the CuCo was 2 S 4 The NiCo 2 S 4 The MnNi 2 S 4 And said ZrS 2 The molar ratio of the used amount of 1: 2.0: 1.7: 1.4, and CuCo 2 S 4 The amount of (A) is 410 g.
Resulting in a metal sulfide reservoir electrode DS 1.
Comparative example 2
This comparative example a metal sulfide energy storage electrode was prepared according to the method of example 1, except that, in step (1), the CuCo was used 2 S 4 The NiCo 2 S 4 The MnNi 2 S 4 And said ZrS 2 The molar ratio of the used amount of the compound is 1: 1.5: 2.0: 1.4 and CuCo 2 S 4 The amount of (B) was 410 g.
Resulting in a metal sulfide reservoir electrode DS 2.
Comparative example 3
This comparative example a metal sulfide energy storage electrode was prepared according to the method of example 1, except that in step (4), metal current collector-1 was replaced with metal current collector-4.
Resulting in a metal sulfide reservoir electrode DS 3.
Test example
The metal sulfide energy storage electrodes prepared in the examples and the comparative examples are assembled into a CR2016 type button cell, the conductivity of the energy storage electrode is detected, and the capacity retention rate and the maximum charge and discharge times of the assembled cell are detected, wherein the specific detection results are shown in Table 1.
Wherein, the conductivity is detected by a conductivity tester (purchased from Shanghai Leimao company, with the model of DDS-11A);
the assembly process of the battery is as follows:
mixing the metal sulfide energy storage electrodes prepared in the examples and the comparative examples with acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, uniformly coating the mixture on a stainless steel foil with the thickness of 75 micrometers, drying the stainless steel foil for 12 hours at 80 ℃ in vacuum (the vacuum degree is negative pressure of 0.1MPa), preparing a circular electrode slice with the diameter of 12mm,
at 100. mu.L of 2mol/L Li 2 SO 4 As an electrolyte, LiMn is used 2 O 4 The prepared circular electrode plate is used as a negative electrode material, and the CR2016 type button cell is assembled.
The detection method of the capacity retention rate comprises the following steps: testing the assembled battery at 25 ℃ by using a battery testing system (Land-CT2001A, purchased from Wuhan blue electric company), respectively testing the first discharge specific capacity of the battery at 1C multiplying power and the discharge specific capacity after 1 cycle, wherein the testing voltage range is 0.7-1.8V, and calculating the capacity retention rate;
wherein, the calculation formula of the capacity retention rate is as follows: (specific discharge capacity after 1 cycle/specific first discharge capacity) x 100%.
The detection method of the maximum charging and discharging times comprises the following steps: under the condition of room temperature, the battery is discharged to 3.0V at the current of 0.2C, then is charged to 4.2V at the constant current of 1C, the cut-off current is 20mA, and is discharged to 3.0V at the current of 0.2C after being placed for 1 hour. The number of charges in which the capacity was 60% of the initial capacity after repeated cycles in accordance with the above-described procedure.
TABLE 1
| Example numbering | Conductivity, S/m | Capacity retention ring ratio,% | Maximum number of charge and discharge times |
| Example 1 | 1.2×10 12 | 99.99 | 10600 |
| Example 2 | 1×10 12 | 98.23 | 10180 |
| Example 3 | 1.15×10 12 | 96.85 | 10320 |
| Example 4 | 0.9×10 12 | 94.35 | 10430 |
| Example 5 | 0.85×10 12 | 93.59 | 10510 |
| Example 6 | 0.82×10 12 | 91.78 | 10290 |
| Example 7 | 0.75×10 12 | 93.62 | 10540 |
| Comparative example 1 | 0.52×10 12 | 81.53 | 9838 |
| Comparative example 2 | 0.5×10 12 | 80.16 | 9850 |
| Comparative example 3 | 0.45×10 12 | 81.72 | 9930 |
The results in table 1 show that the metal sulfide energy storage electrode provided by the invention has the characteristics of high electrode conductivity, good capacity retention rate and long service life, and also has the advantages of high electrochemical reaction efficiency and high charging speed.
The present invention exemplarily provides a schematic view of the structure of the metal current collector in example 1, see fig. 1.
As can be seen from fig. 1, the metal current collector provided by the invention is provided with at least two round holes, so that the electrochemical reaction efficiency of the metal sulfide energy storage electrode can be remarkably improved.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method of making a metal sulfide energy storage electrode, the method comprising:
(1) the molar ratio of the used amount is 1: 1-1.8: 1-1.8: 1-1.8 CuCo 2 S 4 、NiCo 2 S 4 、MnNi 2 S 4 、ZrS 2 Carrying out first contact mixing to obtain a first mixture;
(2) in the presence of a solvent I, carrying out a first contact reaction on the first mixture and sodium sulfide, and sequentially carrying out first cleaning and first drying on a product obtained after the first contact reaction to obtain a first solid material;
(3) in the presence of a solvent II, heating the first solid material to obtain a metal sulfide;
(4) carrying out second contact mixing on the metal sulfide and the conductive adhesive to obtain a coating liquid, and coating the coating liquid on the surface of the metal current collector; wherein the coating thickness of the coating liquid is 0.1-2 mm; at least two round holes are arranged on the metal current collector, and the surface area of the round holes accounts for 10-30% of the total surface area of the metal current collector.
2. The method of claim 1, wherein, in step (1), the CuCo is 2 S 4 The NiCo 2 S 4 The MnNi 2 S 4 And said ZrS 2 The molar ratio of the used amount of the compound is 1: 1-1.5: 1.4-1.8: 1-1.5.
3. The method of claim 1, wherein in step (4), the surface area of the circular holes is 20-30% of the total surface area of the metal current collector.
4. The method according to any one of claims 1 to 3, wherein, in the step (4), the coating liquid is coated to a thickness of 0.5 to 1.5 mm.
5. The method according to any one of claims 1 to 3, wherein in step (2), the conditions of the first contact reaction comprise at least: the temperature is 150 ℃ and 300 ℃, and the time is 3-5 h.
6. The method according to any one of claims 1 to 3, wherein in step (3), the conditions of the heat treatment include at least: the temperature is 200 ℃ and 280 ℃, and the time is 5-10 h.
7. The method according to any one of claims 1 to 3, wherein in the step (4), the mass ratio of the metal sulfide to the conductive adhesive is 3-5: 1.
8. the method of any one of claims 1-3, wherein in step (4), the conditions of the second contacting and mixing comprise at least: the temperature is 20-40 deg.C, the time is 10-60min, and the stirring speed is 40-80 rpm.
9. A metal sulphide energy storage electrode produced by the method of any of claims 1 to 8.
10. Use of the metal sulfide energy storage electrode of claim 9 in an energy storage cell.
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| CN111876748A (en) * | 2020-07-16 | 2020-11-03 | 北京大学深圳研究生院 | Metal sulfide thin film based on organic sulfur precursor and preparation method thereof |
| CN111933904A (en) * | 2020-07-14 | 2020-11-13 | 银隆新能源股份有限公司 | Bimetal sulfide and preparation method thereof, compound and preparation method thereof, lithium-sulfur positive electrode material and lithium-sulfur battery |
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| US5656393A (en) * | 1994-10-21 | 1997-08-12 | W. R. Grace & Co.-Conn. | Flexible electrode, product and process of forming same |
| CN1262533A (en) * | 1999-01-28 | 2000-08-09 | 中国科学院物理研究所 | Secondary lithium battery |
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