Electrode for reversibly storing / releasing manganese ions, battery comprising same and application thereof

Abstract

The invention provides an electrode capable of reversibly storing / releasing manganese ions, a battery comprising the electrode and application of the electrode, and belongs to the technical field of electrochemistry. The electrode capable of reversibly storing / releasing manganese ions comprises a component with a general formula MnXm, wherein M is selected from one or more of Li, Be, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po and At; x is selected from one or more of S, Se and Te; n and m are independently selected from any numerical values larger than 0, and n / m is larger than 0 and smaller than or equal to 10.

Description

Technical Field

[0001] The present invention relates to the field of electrochemical technology, and in particular to an electrode capable of reversibly storing / releasing manganese ions, a battery containing the electrode, and applications thereof. Background Art

[0002] Manganese mineral resources are widely distributed on land and in the ocean, with an average content of about 0.1% in the earth's crust. They have important applications in the fields of steel, nonferrous metallurgy, chemical industry, electronics, batteries, agriculture, medicine, etc. Due to the rich reserves of manganese, mature preparation technology of manganese-containing materials and low cost, manganese is an excellent choice for charge carriers in electrochemical energy storage devices.

[0003] However, there are few choices of electrode materials that support reversible storage / release of manganese ions and their capacity is low. The energy density of manganese-based electrochemical energy storage devices prepared from these materials is also low, far from reaching practical energy density levels.

[0004] Therefore, the development of high-capacity electrodes that can highly reversibly store / release manganese ions has become a key issue in the preparation of high-energy-density manganese-based electrochemical energy storage devices. Summary of the invention

[0005] In view of this, the present invention provides an electrode capable of reversibly storing / releasing manganese ions, a battery comprising the electrode, and applications thereof.

[0006] According to an embodiment of one aspect of the present invention, there is provided an electrode capable of reversibly storing / releasing manganese ions, the electrode comprising a general formula M n X m components; wherein M is selected from one or more of Li, Be, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, and At; X is selected from one or more of S, Se, and Te; n and m are each independently selected from any value greater than 0, and 0<n / m≤10.

[0007] According to an embodiment of the present invention, the above X is selected from S.

[0008] According to an embodiment of the present invention, the M is selected from one or more of Cu and Ni.

[0009] According to an embodiment of the present invention, the above-mentioned n X m The component is Cu n S m, where 0<n / m<2.

[0010] According to an embodiment of the present invention, n / m=1.8.

[0011] According to an embodiment of the present invention, the electrode further includes a conductive agent and a binder.

[0012] According to an embodiment of the present invention, the above-mentioned n X m The weight ratio of the components, the conductive agent and the adhesive is (5~9):(1~3):(0.5~1.5).

[0013] According to another embodiment of the present invention, a manganese ion battery is provided, characterized in that the manganese ion battery comprises the above-mentioned electrode for reversibly storing / releasing manganese ions.

[0014] According to an embodiment of the present invention, the manganese ion battery comprises: an electrolyte, wherein the electrolyte comprises manganese ions with a concentration of 0.01 to 1 mol / L; an electrode, wherein the electrode comprises Cu n S m , where 0<n / m<2.

[0015] According to an embodiment of the present invention, n / m=1.8.

[0016] According to an embodiment of another aspect of the present invention, there is provided a use of the above-mentioned electrode capable of reversibly storing / releasing manganese ions in an electrochemical energy storage device.

[0017] It can be seen from the above technical solutions that the electrode for reversibly storing / releasing manganese ions provided by the present invention, the battery containing the electrode and the application thereof have one or part of the following beneficial effects:

[0018] According to an embodiment of the present invention, the electrode capable of reversibly storing / releasing manganese ions comprises a material having the general formula M n X m By regulating the active substance M n X m The specific composition of the electrode realizes highly reversible manganese ion storage and release performance based on the extraction and embedding of manganese ions in the active material during the charging and discharging process, thereby improving the capacity of the electrode.

[0019] According to an embodiment of the present invention, a manganese ion battery based on an electrode capable of reversibly storing / releasing manganese ions has a high energy density and good cycle stability. The present invention expands the selection range of electrodes for manganese-based electrochemical energy storage devices by developing a class of electrodes capable of reversibly storing / releasing manganese ions. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1The Cu of the embodiment of the present invention is shown 1.8 S charge and discharge mechanism diagram;

[0021] Figure 2 The Cu provided in Example 1 of the present invention is shown 1.8 X-ray diffraction pattern of S;

[0022] Figure 3 The Cu provided in Example 1 of the present invention is shown 1.8 X-ray photoelectron spectrum of S;

[0023] Figure 4 The internal structure diagram of the CR2032 button battery provided in Example 1 of the present invention is shown;

[0024] Figure 5 It shows that the Mn(-)||Cu provided in Example 1 of the present invention 1.8 S (+) Charge and discharge curves of full battery at different current densities;

[0025] Figure 6 The Mn(-)||CuS(+) full cell provided in Example 2 of the present invention has a current density of 50 mA g -1 The charge and discharge curves below;

[0026] Figure 7 The results show that the Mn(-)||NiS2(+) full cell provided in Example 3 of the present invention has a current density of 50 mA g -1 The charge and discharge curves below;

[0027] Figure 8 The Mn(-)||MoS2(+) full cell provided in Comparative Example 2 of the present invention is shown in FIG. -1 The charge and discharge curves below;

[0028] Fig. 9 It shows that the Mn(-)||Cu provided in Example 1 of the present invention 1.8 S (+) full cell at a current density of 500 mAg -1 Cyclic stability curve under

[0029] In the above drawings, the meanings of the reference numerals are as follows:

[0030] 1- negative electrode shell;

[0031] 2-shrapnel;

[0032] 3- Gasket;

[0033] 4- Counter electrode / reference electrode;

[0034] 5- diaphragm;

[0035] 6-working electrode;

[0036] 7- Positive electrode shell. DETAILED DESCRIPTION

[0037] Below, embodiments of the present invention will be described with reference to the accompanying drawings. However, it should be understood that these descriptions are exemplary only and are not intended to limit the scope of the present invention. In the following detailed description, for ease of explanation, many specific details are set forth to provide a comprehensive understanding of embodiments of the present invention. However, it is apparent that one or more embodiments may also be implemented without these specific details. In addition, in the following description, descriptions of known structures and technologies are omitted to avoid unnecessary confusion of concepts of the present invention.

[0038] The terms used herein are only for describing specific embodiments and are not intended to limit the present invention. The term "comprising" used herein indicates the existence of features, steps, operations, but does not exclude the existence or addition of one or more other features.

[0039] In the case of using expressions such as "at least one of A, B, and C, etc.", it should generally be interpreted in accordance with the meaning of the expression generally understood by those skilled in the art (for example, "a system having at least one of A, B, and C" should include but is not limited to a system having A alone, B alone, C alone, A and B, A and C, B and C, and / or A, B, C, etc.). In the case of using expressions such as "at least one of A, B, or C, etc.", it should generally be interpreted in accordance with the meaning of the expression generally understood by those skilled in the art (for example, "a system having at least one of A, B, or C" should include but is not limited to a system having A alone, B alone, C alone, A and B, A and C, B and C, and / or A, B, C, etc.).

[0040] Due to its abundant reserves, mature technology for preparing manganese-containing materials, and low cost, manganese is an excellent choice for use as a charge carrier in electrochemical energy storage devices. However, due to the limited selection and low capacity of electrode materials that support the reversible storage / release of manganese ions, the energy density of manganese-based electrochemical energy storage devices prepared from these materials is also low, far from reaching practical energy density levels. Therefore, the development of high-capacity electrodes that can highly reversibly store / release manganese ions has become a key issue in the preparation of high-energy-density manganese-based electrochemical energy storage devices.

[0041] In the process of realizing the concept of the present invention, it is found that by regulating the specific components of the active material, highly reversible manganese ion storage and release performance can be achieved. To this end, the present invention provides an electrode for reversibly storing / releasing manganese ions, a battery containing the same, and its application.

[0042] Specifically, according to an embodiment of one aspect of the present invention, there is provided an electrode capable of reversibly storing / releasing manganese ions, the electrode comprising a material having a general formula M n X m ; wherein M is selected from one or more of Li, Be, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, At; X is selected from one or more of S, Se, Te; n and m are each independently selected from any value greater than 0, and 0<n / m≤10. Wherein, the symbol " / " represents division. For example, when n is 9 and m is 5, n / m is 1.8.

[0043] According to an embodiment of the present invention, the electrode capable of reversibly storing / releasing manganese ions comprises a material having the general formula M n X m By regulating the active substance M n X m The specific composition of the electrode realizes highly reversible manganese ion storage and release performance based on the extraction and embedding of manganese ions in the active material during the charging and discharging process, thereby improving the capacity of the electrode.

[0044] According to an embodiment of the present invention, n and m may be integers or decimals. For example, n and m are independently selected from 0.5, 1, 1.2, 1.5, 1.8, 2, 2.5, 3, 3.8, 5, 5.2, 10, 10.8, 20, 20.2, 50, 50.2, etc.

[0045] According to an embodiment of the present invention, 0<n / m≤10. Exemplarily, n / m can be 0.5, 0.7, 0.9, 1.0, 1.2, 1.5, 1.8, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5, 10, etc.

[0046] According to an embodiment of the present invention, M is selected from one or more of Li, Be, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, At, which means that M is selected from L 1, 2, 3, 4, 5, ... or 48 of i, Be, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, At. One or more of X selected from S, Se, Te means that X is selected from 1, 2 or 3 of S, Se, Te. Exemplarily, M n X m It can be Li n S m 、Al n S m , Cu n S m 、Ni n S m 、Co n S m , Cu n Se m 、Ni n Se m 、Co n Se m , Cu n Te m 、Ni n Te m 、Co n Te m 、(CoNi) n S m 、(CoNi) n (SSe) m 、(CoNiCo) n (S) m 、(CoNiCo) n (SSeTe) m wait.

[0047] Preferably, M is selected from one or more of Li, Be, Na, Mg, K, Ca, Sc, Cr, Fe, Co, Cu, Ga, Ge, Rb, Sr, Y, Zr, Nb, Ru, Rh, Pd, Ag, Cd, In, Sb, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, and At.

[0048] Further preferably, M is selected from one or more of Cu and Ni. Exemplarily, M may be selected from Cu, Ni or a combination of Cu and Ni.

[0049] Preferably, X is selected from S.

[0050] According to an embodiment of the present invention, a n X m The component is Cu n S m , wherein 0<n / m<2. For example, n / m may be 0.5, 0.7, 1, 1.2, 1.5, 1.7, 1.8, etc.

[0051] In the process of implementing the present invention, it was also found that when working through a single manganese ion embedding mechanism, there are few sites in the electrode for manganese ion embedding, and the capacity provided is small, which is not conducive to further improving the energy density of the final device.

[0052] According to an embodiment of the present invention, a n X m The component is Cu n S m , where n / m=1.8. For example, Cu n S m (n / m=1.8) can be written as Cu 1.8 S, Cu9S5, etc.

[0053] According to an embodiment of the present invention, for Cu n S m For example, in the charging and discharging process, not only the ion embedding process but also the conversion reaction process is involved. 1.8 S as an example, see Figure 1 At the beginning of the discharge process, the manganese ions in the electrolyte are embedded in the Cu 1.8 S, forming manganese compounds (Mn x Cu 1.8 S) provides part of the capacity, and in the subsequent discharge process, it can continue to receive manganese ions in the electrolyte and undergo a conversion reaction to generate a new phase (MnS compound + Cu metal), thereby providing additional capacity. Therefore, compared with the positive electrode with only ion embedding process, Cu nS m (n / m=1.8) The positive electrode has a higher capacity. In the early stage of the charging process, manganese ions gradually escape from the MnS phase and react chemically with Cu metal to generate Mn x Cu 1.8 S intermediate phase, during the subsequent charging process, manganese ions continue to escape and eventually return to Cu 1.8 S. Wherein, x is selected from any value greater than 0.

[0054] According to an embodiment of the present invention, Cu n S m (n / m=1.8) It has a dual manganese ion storage process of manganese ion embedding process and conversion reaction process, which is different from the electrode material that only uses a single manganese ion storage process such as manganese ion embedding process. It not only expands the selection space of manganese storage materials and improves the capacity of active materials of manganese-based electrochemical energy storage devices, but also improves the energy density of manganese-based electrochemical energy storage devices, laying the foundation for the development of high energy density manganese-based electrochemical energy storage devices.

[0055] Furthermore, the inventors have Cu 1.8 S performed theoretical calculations based on density functional theory. Due to the presence of dangling bonds, the optimized Cu 1.8 The state of Cu-S bonds on the S lattice surface has changed significantly compared to before optimization. 1.8 The MS (M stands for metal) bond lengths on the surface of the S crystal were statistically analyzed and the results showed that Cu 1.8 The bond length distribution of S is relatively wide, especially after structural optimization. 1.8 S has more possible active sites and higher reactivity, thus providing a more electrochemically active surface for Mn replacement reaction. 1.8 The Gibbs free energy change (ΔG) of the manganese substitution reaction on the S lattice surface shows that Cu 1.8 The ΔG value of the manganese replacement reaction of S is small or negative. 1.8 The surface of S is more susceptible to manganese substitution reaction.

[0056] In addition, the Cu 1.8 S and Cu substituted by one Mn atom 1.8 The p-band density of states (DOS) of S atoms in S (denoted as Mn-CS) was used to detect the Cu 1.8 The changes in the internal coordination environment of S. The results show that Cu 1.8 The p-band center of the S atom in S rises from -2.57 eV to -2.22 eV, which is conducive to the further adsorption and substitution reaction of manganese. In order to confirm this hypothesis, the inventors further calculated the adsorption energy of manganese ions. 1.8The adsorption energy on the S crystal surface is lower, which indicates that Cu 1.8 S crystals have a high manganese ion adsorption capacity. In addition, the adsorption energy of Mn-CS after Mn substitution is reduced to -2.83 eV, which indicates that the substitution of manganese atoms promotes the adsorption of Cu 1.8 The adsorption process of S on manganese ions is consistent with the calculated results of state density.

[0057] Therefore, the theoretical calculation results show that the inclusion of Cu 1.8 The positive electrode of S has better comprehensive performance.

[0058] According to an embodiment of the present invention, Cu n S m (n / m=1.8) can be prepared by the following method: dissolving CuCl2·2H2O in ethylene glycol at 100°C~140°C to obtain an ethylene glycol solution of CuCl2; dissolving thiourea in ethylene glycol at 100°C~140°C to obtain an ethylene glycol solution of thiourea; adding the ethylene glycol solution of CuCl2 to the ethylene glycol solution of thiourea to obtain a mixed solution; sealing the mixed solution into a reactor, reacting at 120°C~160°C for 4~8h, washing, and drying to obtain an intermediate; heating the intermediate to 300°C~400°C at a heating rate of 2°C / min~8°C / min under a protective atmosphere, sintering for 1~3h, and then naturally cooling to room temperature to obtain Cu n S m (n / m=1.8).

[0059] According to an embodiment of the present invention, the electrode further includes a conductive agent and a binder.

[0060] The present invention does not limit the type of conductive agent, and any material with conductive properties can be used as the conductive agent in the present application. For example, the conductive agent can be one or more of Ketjen black, acetylene black, carbon black, graphite, graphene, carbon fiber, etc.

[0061] The present invention does not limit the type of adhesive, and any material with adhesive properties can be used as the adhesive in the present application. For example, the adhesive can be one or more of polyvinylidene fluoride, polytetrafluoroethylene, water-soluble rubber, and cellulose.

[0062] According to an embodiment of the present invention, a n X m The weight ratio of the components, the conductive agent and the binder is (5-9): (1-3): (0.5-1.5). n X mThe weight ratio of the components, the conductive agent and the adhesive can be 5:1:0.5, 5:2:1, 5:3:1.5, 7:2:1, 9:1:0.5, 9:2:1, 9:3:1.5, etc.

[0063] According to another embodiment of the present invention, a manganese ion battery is provided. The manganese ion battery includes the above-mentioned electrode that can reversibly store / release manganese ions.

[0064] According to an embodiment of the present invention, a manganese ion battery based on an electrode capable of reversibly storing / releasing manganese ions has a high energy density and good cycle stability.

[0065] According to an embodiment of the present invention, M can be selected from one or more of Li, Be, Na, Mg, K, Ca, Sc, Cr, Fe, Co, Cu, Ga, Ge, Rb, Sr, Y, Zr, Nb, Ru, Rh, Pd, Ag, Cd, In, Sb, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, At. Preferably, M is selected from one or more of Cu, Ni, and Co.

[0066] According to an embodiment of the present invention, X may be selected from S.

[0067] According to an embodiment of the present invention, a manganese ion battery comprises: an electrolyte, wherein the electrolyte comprises manganese ions at a concentration of 0.01 to 1 mol / L. For example, the concentration of manganese ions in the electrolyte may be 0.01 mol / L, 0.02 mol / L, 0.05 mol / L, 0.07 mol / L, 0.1 mol / L, 0.2 mol / L, 0.5 mol / L, 0.7 mol / L, 1 mol / L, etc.

[0068] According to an embodiment of the present invention, a manganese ion battery includes an electrode, wherein the electrode includes Cu n S m , wherein 0<n / m<2. Preferably, the electrode comprises Cu n S m , where n / m=1.8.

[0069] According to another embodiment of the present invention, there is provided a use of the above-mentioned electrode capable of reversibly storing / releasing manganese ions in electrochemical energy storage devices, especially batteries and capacitors.

[0070] The present invention expands the selection range of electrodes for manganese-based electrochemical energy storage devices by developing a type of electrode capable of reversibly storing / releasing manganese ions.

[0071] The following lists a number of specific embodiments to illustrate the technical solution of the present invention in detail. It should be noted that the specific embodiments below are only used for illustration and are not used to limit the present invention.

[0072] Example 1

[0073] This embodiment provides an electrode that can reversibly store / release manganese ions, and a manganese ion battery is assembled using the electrode.

[0074] The electrode for reversibly storing / releasing manganese ions provided in this embodiment includes Cu 1.8 S. Among them, Cu 1.8 The preparation method of S comprises the following steps: weigh 2.0 g CuCl2·2H2O and 3.6 g thiourea, and dissolve each in 80 mL of ethylene glycol at 120°C. After both solutions are completely dissolved into clear solutions, slowly pour the CuCl2 solution into the thiourea solution. After the transfer is completed, the mixed solution is stirred at 120°C for 10 minutes and then transferred to the inner tank of a reactor with a volume of 200 mL. Subsequently, the inner tank containing the reaction solution is packaged with an outer liner, and reacted at a temperature of 140°C in a forced air drying oven for 6 hours. After natural cooling, the reacted black suspension is poured into a suction filtration container, and washed three times with deionized water and anhydrous ethanol to obtain a black solid product. Subsequently, the washed product is placed in a vacuum drying oven and dried at 80°C for 8 hours, and then transferred to a tubular furnace. In an atmosphere of high-purity argon, the heating rate is 5°C / min, and the temperature is sintered at 350°C for 2 hours and then naturally cooled to room temperature to obtain the final Cu 1.8 S product.

[0075] The Cu provided in this embodiment 1.8 The S product was subjected to X-ray diffraction (XRD) test, and the test results were as follows Figure 2 As shown. Figure 2 Analysis shows that the Cu 1.8 The X-ray diffraction pattern of the S product is very consistent with the standard card numbered PDF#47-1748, indicating that the phase of the prepared copper metal sulfide is Cu 1.8 S.

[0076] The Cu provided in this embodiment 1.8 The S product was subjected to X-ray photoelectron spectroscopy (XPS) testing, and the test results were as follows Figure 3 As shown. Figure 3Analysis shows that both Cu and S elements present two different bonding states. From the high-resolution spectrum results of Cu 2p, it can be seen that the main peaks centered at 932.5 eV and 952.3 eV prove that most of the copper ions in the prepared copper metal sulfide are in the +1 valence state. The other set of double peaks located at 933.8 eV and 953.5 eV proves that there are trace amounts of +2 valence copper ions in the prepared copper metal sulfide. In the S 2p high-resolution spectrum, the two characteristic double peaks centered at 161.7 eV and 162.8 eV and centered at 163.7 eV and 164.8 eV indicate the coexistence of Cu-S and SS bonds in the prepared metal sulfide.

[0077] The electrode for reversible storage / release of manganese ions provided in this embodiment can be prepared by the following method: weigh 210 mg of the obtained Cu 1.8 S product, 60 mg Ketjen black and 30 mg polyvinylidene fluoride were transferred to a mortar and ground evenly, then poured into a 100 mL ball ink tank, and 4 mL N-methylpyrrolidone was added, and the slurry was prepared by ball milling at 250 r / min for 2 hours. Subsequently, the prepared slurry was evenly scraped on the rough surface of a single-sided rough copper foil with a thickness of 20 microns. After drying in a vacuum drying oven at 80°C for 2 hours, the large electrode sheet coated with the active material was blasted into a prototype electrode sheet with a diameter of 12 mm using a blasting machine to obtain Cu 1.8 S positive electrode.

[0078] This embodiment also provides a manganese ion battery, which is Mn(-) || Cu 1.8 S (+) Full battery.

[0079] Figure 4 The exploded view of the CR2032 button battery used in Example 1 of the present invention is schematically shown. Figure 4 As shown, in a glove box where the water and oxygen content was less than 0.1 ppm, a manganese sheet was used as the negative electrode 4, Cu 1.8 The S pole piece is the positive electrode 6, 70 μL organic electrolyte for organic manganese metal full battery is the electrolyte, a glass fiber membrane (GF / A) with a diameter of 19 mm is the separator 5, a gasket 3 with a thickness of 0.5 mm and a spring 2 with a height of 1.1 mm are space fillers, and the negative electrode shell 1 with a diameter of 18 mm and the positive electrode shell 7 with a diameter of 20 mm are used for assembly, wherein the spring 2, gasket 3, positive electrode shell 7 and negative electrode shell 1 can be made of stainless steel. Figure 1 The structure shown is assembled into a 304 stainless steel button model CR2032 Mn(-) || Cu 1.8 S (+) Full battery.

[0080] The electrolyte was prepared by the following method: 20 mL of 0.03 mol / L bis(trifluoromethylsulfonylimide) manganese salt, 0.06 mol / L anhydrous manganese chloride and 0.03 mol / L anhydrous aluminum chloride were prepared in a glove box where the water and oxygen contents were all lower than 0.1 ppm, and the solution was an electrolyte of tetrahydrofuran.

[0081] Example 2

[0082] This embodiment provides an electrode that can reversibly store / release manganese ions, and a manganese ion battery is assembled using the electrode.

[0083] The electrode for reversibly storing / releasing manganese ions provided in this embodiment includes CuS.

[0084] The preparation method of the electrode for reversibly storing / releasing manganese ions provided in this embodiment is similar to that in embodiment 1, the Cu 1.8 S was replaced with an equal weight of CuS.

[0085] This embodiment also provides a manganese ion battery, which is a Mn(-) || CuS (+) full battery. The assembly method of the battery provided in this embodiment and the preparation of the electrolyte are referred to in Example 1, except that in this embodiment, the positive electrode 6 is replaced by the CuS electrode sheet prepared in this embodiment.

[0086] Example 3

[0087] This embodiment provides an electrode that can reversibly store / release manganese ions, and a manganese ion battery is assembled using the electrode.

[0088] The electrode for reversibly storing / releasing manganese ions provided in this embodiment includes NiS2.

[0089] The preparation method of the electrode for reversibly storing / releasing manganese ions provided in this embodiment is similar to that in embodiment 1, the Cu 1.8 S is replaced by an equal weight of NiS2.

[0090] This embodiment also provides a manganese ion battery, which is a Mn(-) || NiS2 (+) full battery. The assembly method of the battery provided in this embodiment and the preparation of the electrolyte are referred to in Example 1, except that in this embodiment, the positive electrode 6 is replaced by the NiS2 electrode sheet prepared in this embodiment.

[0091] Comparative Example 1

[0092] This comparative example provides an electrode that can reversibly store / release manganese ions, and a manganese ion battery is assembled using the electrode.

[0093] The electrode for reversibly storing / releasing manganese ions provided in this comparative example includes MoS2.

[0094] The preparation method of the electrode for reversibly storing / releasing manganese ions provided in this comparative example is similar to that in Example 1, the Cu 1.8 S is replaced with an equal weight of MoS2.

[0095] This comparative example also provides a manganese ion battery, which is a Mn(-) || MoS2 (+) full battery. The assembly method of the battery provided in this example and the preparation of the electrolyte are referred to Example 1, except that in this example, the positive electrode 6 is replaced by the MoS2 electrode sheet prepared in this example.

[0096] The electrochemical performance of the following full cells was tested.

[0097] The assembled button battery was clamped on a fixture on a battery testing system, and the charge and discharge curves of the full batteries provided in Examples 1 to 3 and Comparative Example 1 were tested. Figure 5 It shows that the Mn(-)||Cu provided in Example 1 of the present invention 1.8 S (+) Charge and discharge curves of full battery at different current densities; Figure 6 The Mn(-)||CuS(+) full cell provided in Example 2 of the present invention has a current density of 50 mA g -1 The charge and discharge curves below; Figure 7 The results show that the Mn(-)||NiS2(+) full cell provided in Example 3 of the present invention has a current density of 50 mA g -1 The charge and discharge curves below; Figure 8 The Mn(-)||MoS2(+) full cell provided in Comparative Example 1 of the present invention is shown in FIG. -1 The charge and discharge curves below.

[0098] Depend on Figure 5~Figure 8 Analysis shows that, compared with Comparative Example 1, the full battery provided by the present invention has a higher manganese ion storage capacity.

[0099] Depend on Figure 5 Analysis shows that the Cu 1.8 The positive electrode of S is at 20 mA g -1 , 100 mA g -1 , 200mA g -1 and 500 mA g -1 At current densities of 218 mAh g -1 , 189.8 mAh g -1 , 145.2 mAh g -1and 82.2 mAh g -1 The discharge capacity of Cu 1.8 The positive electrode of S has good rate performance.

[0100] The assembled button cell was clamped on a fixture on a battery testing system, and the cycle performance curve of the full battery provided in Example 1 was tested. Fig. 9 It shows that the Mn(-)||Cu provided in Example 1 of the present invention 1.8 S (+) full cell at a current density of 500 mA g -1 The cyclic stability curve.

[0101] Depend on Fig. 9 Analysis shows that even at 500 mA g -1 Under high current density, the prepared Mn (-)||Cu 1.8 The S(+) full battery can still cycle stably for more than 400 times.

[0102] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made to the technical method by any technician familiar with the art within the spirit and principle of the present invention is still included in the protection scope of the technical solution of the present invention.

Claims

1. An electrode for reversibly storing / releasing manganese ions, characterized in that: The electrode comprises a general formula M n X m Components of Wherein, M is selected from one or more of Li, Be, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, and At; X is selected from one or more of S, Se, and Te; n and m are each independently selected from any value greater than 0, and 0<n / m≤10.

2. The electrode according to claim 1, characterized in that The X is selected from S.

3. The electrode according to claim 1 or 2, characterized in that The M is selected from one or more of Cu and Ni.

4. The electrode according to claim 3, characterized in that The general formula M n X m The component is Cu n S m , where 0<n / m<2.

5. The electrode according to claim 4, characterized in that n / m=1.

8.

6. The electrode according to claim 1 or 2, characterized in that: The electrode also includes a conductive agent and a binder; The general formula M n X m The weight ratio of the components, the conductive agent and the adhesive is (5~9):(1~3):(0.5~1.5).

7. A manganese ion battery, characterized in that: The manganese ion battery comprises the electrode capable of reversibly storing / releasing manganese ions according to any one of claims 1 to 6.

8. The battery according to claim 7, characterized in that The manganese ion battery comprises: An electrolyte, wherein the electrolyte comprises manganese ions at a concentration of 0.01 to 1 mol / L; The electrode comprises Cu n S m , where 0<n / m<2.

9. The battery according to claim 8, characterized in that n / m=1.

8.

10. Use of an electrode capable of reversibly storing / releasing manganese ions according to any one of claims 1 to 6 in an electrochemical energy storage device.

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