Reversible storage / release of manganese ions electrode, battery comprising same and applications thereof

Abstract

The application provides a reversible manganese ion storage / release electrode, a battery comprising the same and an application thereof, and belongs to the technical field of electrochemistry. The reversible manganese ion storage / release electrode comprises a component with a general formula of 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 and At; X is selected from one or more of S, Se and Te; and n and m are each independently selected from any numerical value greater than 0, and 0 < n / m < 10.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of electrochemistry, in particular to a reversible manganese ion storage / release electrode, a battery comprising the same and applications thereof. BACKGROUND

[0002] Manganese is widely distributed in land and sea, and its average content in the earth's crust is about 0.1%. It has important applications in the fields of steel, non-ferrous metallurgy, chemical industry, electronics, batteries, agriculture, medicine, etc. Due to its abundant reserves, mature preparation technology and low cost, manganese is an excellent choice as a charge carrier for electrochemical energy storage devices.

[0003] However, there are few electrode materials that can reversibly store / release manganese ions, and the capacity of these materials is low. The energy density of manganese-based electrochemical energy storage devices prepared from these materials is also low, far from the practical energy density level.

[0004] Therefore, developing an electrode that can reversibly store / release manganese ions with high capacity is a key problem for preparing high-energy-density manganese-based electrochemical energy storage devices. SUMMARY

[0005] In view of the above, the present application provides a reversible manganese ion storage / release electrode, a battery comprising the same and applications thereof.

[0006] According to an embodiment of one aspect of the present application, a reversible manganese ion storage / release electrode is provided, which comprises a component having a general formula of 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, m are each independently selected from any number greater than 0, and 0

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

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

[0009] According to an embodiment of the present application, the component having a general formula of M n X m is Cu n S mwherein 0 < n / m < 2.

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

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

[0012] According to an embodiment of the present application, the electrode comprises a component having a general formula of M n X m The weight ratio of the component having a general formula of M n X m , the conductive agent and the binder is (5-9):(1-3):(0.5-1.5).

[0013] According to an embodiment of another aspect of the present application, a manganese ion battery is provided, characterized in that the manganese ion battery comprises the electrode capable of reversibly storing and releasing manganese ions.

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

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

[0016] According to an embodiment of another aspect of the present application, the electrode capable of reversibly storing and releasing manganese ions is applied in an electrochemical energy storage device.

[0017] It can be seen from the above technical solution that the electrode capable of reversibly storing and releasing manganese ions, the battery comprising the electrode and the application of the electrode have one or some of the following beneficial effects:

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

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

[0020] Figure 1CuS provided by the embodiment of the present application 1.8 S charge-discharge mechanism diagram

[0021] Figure 2 CuS provided by the embodiment 1 of the present application 1.8 X-ray diffraction pattern of S

[0022] Figure 3 CuS provided by the embodiment 1 of the present application 1.8 X-ray photoelectron spectrogram of S

[0023] Figure 4 CR2032 button cell internal structure schematic diagram provided by the embodiment 1 of the present application

[0024] Figure 5 Mn(-)||CuS (+) full cell under different current densities provided by the embodiment 1 of the present application 1.8 Charge-discharge curve

[0025] Figure 6 Mn(-)||CuS (+) full cell under the current density of 50 mA g-1 provided by the embodiment 2 of the present application -1 Charge-discharge curve

[0026] Figure 7 Mn(-)||NiS2 (+) full cell under the current density of 50 mA g-1 provided by the embodiment 3 of the present application -1 Charge-discharge curve

[0027] Figure 8 Mn(-)||MoS2 (+) full cell under the current density of 50 mA g-1 provided by the comparative example 2 of the present application -1 Charge-discharge curve

[0028] Figure 9 Mn(-)||CuS (+) full cell under the current density of 500 mA g-1 provided by the embodiment 1 of the present application 1.8 Cycle stability curve -1

[0029] In the above-mentioned drawings, the meanings of the reference signs are as follows:

[0030] 1-negative electrode shell

[0031] 2-spring

[0032] 3-gasket

[0033] 4-counter electrode / reference electrode

[0034] 5-separator ​

[0035] 6 - working electrode;

[0036] 7 - positive electrode case. DETAILED DESCRIPTION

[0037] Hereinafter, embodiments of the present application will be described with reference to the accompanying drawings. It is to be understood, however, that these descriptions are merely exemplary and are intended to illustrate the scope of the present application, not to limit it. In the following detailed description of the embodiments of the present application, numerous specific details are set forth in order to provide a thorough understanding of the embodiments of the present application. However, it will be apparent to one skilled in the art that the embodiments of the present application can be practiced without these specific details. In other instances, well-known structures and functions have not been described in detail in order to avoid obscuring the concepts of the present application.

[0038] The terms used herein are merely used to describe specific embodiments, and are not intended to limit the present application. The term "include" used herein indicates the presence of a feature, step, operation, but does not exclude the presence 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", it should generally be interpreted to include at least one of each item enumerated, but not only one of each item enumerated, in the context of the present application. In other words, the expression "at least one of A, B, and C" should be interpreted to mean that A alone, B alone, C alone, a combination of A and B, a combination of A and C, a combination of B and C, or a combination of A and B and C are all included. In the case of using expressions such as "at least one of A, B, or C", it should generally be interpreted to include at least one of each item enumerated, but not only one of each item enumerated, in the context of the present application. In other words, the expression "at least one of A, B, or C" should be interpreted to mean that A alone, B alone, C alone, a combination of A and B, a combination of A and C, a combination of B and C, or a combination of A and B and C are all included.

[0040] Manganese is an excellent choice for a charge carrier of an electrochemical energy storage device due to its abundant reserves, mature preparation technology, and low cost. However, the energy density of a manganese-based electrochemical energy storage device prepared from an electrode material capable of reversibly storing and releasing manganese ions is low due to the limited selection of the electrode material and low capacity. Therefore, developing an electrode capable of highly reversibly storing and releasing manganese ions and having high capacity is a key problem for preparing a manganese-based electrochemical energy storage device having high energy density.

[0041] It is found in the process of implementing the concept of the present application that highly reversible manganese ion storage and release performance can be achieved by regulating the specific components of an active material. In this regard, the present application provides an electrode capable of reversibly storing and releasing manganese ions, a battery comprising the same, and applications thereof.

[0042] Specifically, according to an embodiment of one aspect of the present application, there is provided a reversible manganese ion storage / release electrode, which comprises a component having a general formula of 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, m are each independently selected from any value greater than 0, and 0 < n / m < 10. The symbol " / " means division. For example, when n is 9 and m is 5, n / m is 1.8.

[0043] According to an embodiment of the present application, the reversible manganese ion storage / release electrode comprises a component having a general formula of M n X m By regulating the specific composition of the active substance M n X m Based on the extraction and intercalation of manganese ions in the active substance during the charging and discharging process, a highly reversible manganese ion storage and release performance is achieved, and the capacity of the electrode is improved.

[0044] According to an embodiment of the present application, n and m can be integers or decimals. For example, n and m are each 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 application, 0 < n / m < 10, for example, 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 embodiments of the present application, M 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 means M is selected from 1, 2, 3, 4, 5, ···, or 48 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 selected from one or more of S, Se, Te means X is selected from 1, 2, or 3 of S, Se, Te. Exemplarily, M n X m may 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 , etc.

[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] More 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, it has the general formula M n X m The component is Cu n S m Where 0 < n / m < 2. For example, n / m can be 0.5, 0.7, 1, 1.2, 1.5, 1.7, 1.8, etc.

[0051] In the process of realizing this invention, it was also discovered that when operating through a single manganese ion intercalation mechanism, there are few sites in the electrode available for manganese ion intercalation, resulting in a small capacity and hindering further improvement in the energy density of the final device.

[0052] According to an embodiment of the present invention, it has the general formula M 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 (n / m=1.8), the charging and discharging process involves not only ion intercalation but also conversion reactions. Taking Cu as an example... 1.8 For example, see S. Figure 1 In the initial stage of the discharge process, manganese ions in the electrolyte are inserted into Cu. 1.8 In S, manganese-modified compounds (Mn) are formed. x Cu 1.8 The S phase provides a portion of the capacity, and during subsequent discharge, it can continue to receive manganese ions from the electrolyte and undergo a conversion reaction to generate a new phase (MnS compound + Cu metal), thus providing additional capacity. Therefore, compared to a cathode that only involves ion intercalation, Cu... nS m (n / m=1.8) has higher capacity. In the initial stage of the charging process, manganese ions are gradually removed from the MnS phase and chemically react with Cu metal to form Mn x Cu 1.8 S intermediate phase. In the subsequent charging process, manganese ions continue to be removed and eventually return to Cu 1.8 S. Wherein x is selected from any value greater than 0.

[0054] According to the embodiments of the present application, Cu n S m (n / m=1.8) has a dual manganese ion storage process of manganese ion intercalation process and conversion reaction process, which is different from the electrode material of only manganese ion intercalation process. It not only expands the selection space of manganese storage materials and improves the capacity of manganese-based electrochemical energy storage device active materials, but also improves the energy density of manganese-based electrochemical energy storage devices, and lays a foundation for developing high-energy density manganese-based electrochemical energy storage devices.

[0055] Further, the inventors have carried out theoretical calculations based on density functional theory on Cu 1.8 S. Due to the existence of dangling bonds, the state of Cu-S bond on the surface of the optimized Cu 1.8 S lattice has changed greatly compared with that before optimization. The M-S (M represents metal) bond length on the surface of the Cu 1.8 S crystal before and after structure optimization is counted, and the results show that the bond length distribution of Cu 1.8 S is wide, especially after structure optimization. Therefore, Cu 1.8 S has more possible active sites and higher reaction activity, thereby providing a more electrochemically active surface for Mn displacement reaction. The Gibbs free energy change (ΔG) of manganese displacement reaction on the surface of Cu 1.8 S lattice is further calculated, and the results show that the ΔG value of manganese displacement reaction of Cu 1.8 S is small or negative, and the manganese displacement reaction is more likely to occur on the surface of Cu 1.8 S.

[0056] In addition, the p-band density of states (DOS) of S atoms in Cu 1.8 S and Cu 1.8 S (denoted as Mn-CS) after being replaced by one manganese atom is evaluated to detect the change of the coordination environment inside Cu 1.8 S before and after manganese replacement. The results show that the p-band center of S atoms in Cu 1.8 S rises from -2.57 eV to -2.22 eV, which is conducive to further adsorption and displacement reaction of manganese. In order to verify this hypothesis, the inventors have further calculated the adsorption energy of manganese ions. Cu 1.8The adsorption energy of the S crystal surface is lower, which indicates that Cu 1.8 The S crystal has a higher adsorption capacity for Mn ions. In addition, the adsorption energy of Mn-CS after Mn substitution is reduced to -2.83 eV, which indicates that the substitution of Mn atoms promotes the adsorption of Mn ions on the Cu 1.8 S surface. This is in good agreement with the calculation results of the density of states.

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

[0058] According to an embodiment of the present application, 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 a CuCl2 ethylene glycol solution; dissolving thiourea in ethylene glycol at 100°C~140°C to obtain a thiourea ethylene glycol solution; adding the CuCl2 ethylene glycol solution to the thiourea ethylene glycol solution to obtain a mixed solution; sealing the mixed solution in a reaction kettle and reacting at 120°C~160°C for 4~8h, washing, and drying to obtain an intermediate; sintering the intermediate at a temperature of 300°C~400°C at a temperature increasing rate of 2°C / min~8°C / min for 1~3h under a protective atmosphere and then naturally decreasing to room temperature to obtain Cu n S m (n / m=1.8).

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

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

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

[0062] According to an embodiment of the present application, the weight ratio of the component having the general formula M n X m , the conductive agent and the binder is (5~9):(1~3):(0.5~1.5). Exemplarily, the weight ratio of the component having the general formula M n X mThe weight ratio of the components, the conductive agent and the binder 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 an embodiment of another aspect of the present application, there is provided a manganese ion battery comprising the reversible manganese ion storage / release electrode.

[0064] According to an embodiment of the present application, the manganese ion battery based on the reversible manganese ion storage / release electrode has a high energy density and good cycle stability.

[0065] According to an embodiment of the present application, 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, Co.

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

[0067] According to an embodiment of the present application, the manganese ion battery comprises an electrolyte, wherein the electrolyte comprises manganese ions at a concentration of 0.01-1 mol / L. Exemplarily, the concentration of the manganese ions in the electrolyte can 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 application, the manganese ion battery comprises an electrode, wherein the electrode comprises Cu n S m , wherein 0 n S m , wherein n / m=1.8.

[0069] According to an embodiment of another aspect of the present application, there is provided a use of the reversible manganese ion storage / release electrode in an electrochemical energy storage device, in particular a battery and a capacitor.

[0070] The present application expands the selection range of the electrode of the manganese-based electrochemical energy storage device by developing a kind of electrode capable of reversible storage / release of manganese ions.

[0071] The technical solutions of the present application are described in detail below by listing a plurality of specific embodiments. It should be noted that the specific embodiments below are only for illustration and do not limit the present application.

[0072] Embodiment 1

[0073] The present embodiment provides an electrode capable of reversibly storing and releasing manganese ions, and a manganese ion battery is assembled using the electrode.

[0074] The electrode capable of reversibly storing and releasing manganese ions provided by the present embodiment includes Cu 1.8 S. Wherein, the Cu 1.8 The preparation method of the Cu 1.8 S includes the following steps: weighing 2.0 g of CuCl2·2H2O and 3.6 g of thiourea, and dissolving 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, and after the transfer is complete, continue to stir the mixed solution at 120°C for 10 minutes, and then transfer it to the inner container of a 200 mL reaction kettle. Then, the inner container containing the reaction solution is packaged with an outer liner, and the reaction is carried out in a forced air drying oven at a temperature of 140°C for 6 hours. After natural cooling, pour the black suspension after reaction into a suction filtration container, and wash with deionized water and anhydrous ethanol respectively for three times to obtain a black solid product. Then, the washed product is placed in a vacuum drying oven at 80°C for 8 hours, and then transferred to a tube furnace, sintered at a temperature of 350°C under an atmosphere of high-purity argon at a heating rate of 5°C / min for 2 hours, and then naturally cooled to room temperature to obtain the final Cu 1.8 S product.

[0075] The Cu 1.8 S product provided by the present embodiment is subjected to X-ray diffraction (XRD) test, and the detection result is shown in Figure 2 By analyzing Figure 2 , it can be seen that the X-ray diffraction pattern of the Cu 1.8 S product provided by the present embodiment is very consistent with the standard card numbered as PDF#47-1748 in the standard card, indicating that the phase of the prepared copper metal sulfide is Cu 1.8 S.

[0076] The Cu 1.8 S product provided by the present embodiment is subjected to X-ray photoelectron spectroscopy (XPS) test, and the detection result is shown in Figure 3 By analyzing Figure 3Analysis reveals that both Cu and S exhibit two distinct bonding states. The high-resolution Cu 2p spectrum, with its main peaks centered at 932.5 eV and 952.3 eV, indicates that most copper ions in the prepared copper sulfide are in the +1 valence state. A second set of doublets at 933.8 eV and 953.5 eV demonstrates the presence of trace amounts of +2 valence copper ions in the prepared copper sulfide. In the S 2p high-resolution spectrum, two characteristic doublets centered at 161.7 eV and 162.8 eV, and another at 163.7 eV and 164.8 eV, indicate the coexistence of Cu-S and SS bonds in the prepared metal sulfide.

[0077] The reversible manganese ion storage / release electrode provided in this embodiment can be prepared by the following method: weighing 210 mg of obtained Cu 1.8 Product S, 60 mg of Ketjen Black, and 30 mg of polyvinylidene fluoride were transferred to a mortar and ground evenly. The mixture was then poured into a 100 mL ball mill container, and 4 mL of N-methylpyrrolidone was added. The mixture was ball-milled at 250 r / min for 2 hours to prepare a slurry. The prepared slurry was then evenly coated onto the roughened surface of a single-sided roughened copper foil with a thickness of 20 micrometers. After drying in a vacuum drying oven at 80°C for 2 hours, the large electrode sheet coated with the active material was punched into a prototype electrode sheet with a diameter of 12 mm using a punching machine to obtain Cu. 1.8 S-positive electrode plate.

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

[0079] Figure 4 An exploded view of the CR2032 button cell used in Embodiment 1 of the present invention is shown schematically, with reference to... Figure 4 As shown, in a glove box where the water and oxygen content are both below 0.1 ppm, using manganese sheets as the negative electrode 4, Cu 1.8 The S-electrode is the positive electrode 6. The 70 μL organic-manganese metal full cell uses an organic electrolyte. A 19 mm diameter glass fiber membrane (GF / A) serves as the separator 5. A 0.5 mm thick gasket 3 and a 1.1 mm high spring sheet 2 are used as space fillers. The assembly is completed using an 18 mm diameter negative electrode shell 1 and a 20 mm diameter positive electrode shell 7. The spring sheet 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 CR2032 model 304 stainless steel button (Mn(-) ||Cu). 1.8 S (+) full cell.

[0080] The electrolyte is prepared by the following method: in a glove box with water oxygen content less than 0.1 ppm, 20 mL of electrolyte is prepared with 0.03 mol / L of bis(trifluoromethylsulfonylimide) manganese salt, 0.06 mol / L of anhydrous manganese chloride and 0.03 mol / L of anhydrous aluminum chloride as solutes, and tetrahydrofuran as a solution.

[0081] Example 2

[0082] The example provides an electrode capable of reversibly storing and releasing manganese ions, and a manganese ion battery is assembled using the electrode.

[0083] The electrode capable of reversibly storing and releasing manganese ions provided by the example comprises CuS.

[0084] The preparation method of the electrode capable of reversibly storing and releasing manganese ions provided by the example refers to that of Example 1, except that CuS is used instead of CuS in Example 1. 1.8 S in Example 1.

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

[0086] Example 3

[0087] The example provides an electrode capable of reversibly storing and releasing manganese ions, and a manganese ion battery is assembled using the electrode.

[0088] The electrode capable of reversibly storing and releasing manganese ions provided by the example comprises NiS2.

[0089] The preparation method of the electrode capable of reversibly storing and releasing manganese ions provided by the example refers to that of Example 1, except that NiS2 is used instead of CuS in Example 1. 1.8 S in Example 1.

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

[0091] Comparative Example 1

[0092] The comparative example provides an electrode capable of reversibly storing and releasing manganese ions, and a manganese ion battery is assembled using the electrode.

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

[0094] The preparation method of the reversible manganese ion storage / release electrode provided in this comparative example is the same as that in Example 1, except that the Cu in Example 1 is used instead of 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 cell. The assembly method and electrolyte preparation of the battery provided in this embodiment are the same as in Example 1, except that the positive electrode 6 is replaced with the MoS2 electrode sheet prepared in this embodiment.

[0096] The electrochemical performance of the full cell was tested below.

[0097] The assembled button cell battery is clamped onto the fixture on the battery testing system, and the charge-discharge curves of the full cells provided in Examples 1-3 and Comparative Example 1 are tested. Figure 5 The Mn(-)||Cu provided in Embodiment 1 of the present invention is shown. 1.8 Charge-discharge curves of the S (+) full cell at different current densities; Figure 6 The Mn(-)||CuS(+) full cell provided in Example 2 of the present invention is shown at a current density of 50 mA g. -1 The charge / discharge curves are as follows; Figure 7 The Mn(-)||NiS2(+) full cell provided in Example 3 of the present invention is shown at a current density of 50 mA g. -1 The charge / discharge curves are as follows; Figure 8 The Mn(-)||MoS2(+) full cell provided in Comparative Example 1 of the present invention is shown at a current density of 50 mA g. -1 The charge / discharge curves are shown below.

[0098] Depend on Figures 5 to 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 provided in Example 1 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, respectively, -1 189.8 mAh g -1 145.2 mAh g -1and 82.2 mAh g -1 The discharge specific capacity indicates that Cu is present. 1.8 The positive electrode of S has good rate performance.

[0100] The assembled button cell battery is clamped onto the fixture on the battery testing system to test the cycle performance curve of the full battery provided in Example 1. Figure 9 The Mn(-)||Cu provided in Embodiment 1 of the present invention is shown. 1.8 The S (+) full cell at a current density of 500 mA g -1 The cyclic stability curve is shown below.

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

[0102] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, or improvements made by those skilled in the art to the technical methods within the spirit and principles of the present invention shall still be included within the protection scope of the technical solution of the present invention.

Claims

1. A manganese-ion battery, characterized in that, The manganese-ion battery includes an electrode that reversibly stores / releases manganese ions, the electrode comprising a general formula M n X m Components; The one with general formula M n X m The component is Cu n S m Where n / m = 1.8; The electrode involves both manganese ion insertion and conversion reactions during the charging and discharging process of the manganese ion battery.

2. The manganese-ion battery according to claim 1, characterized in that, The electrode also includes a conductive agent and a binder; The one with 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).

3. The manganese-ion battery according to claim 1 or 2, characterized in that, The manganese-ion battery also includes: The electrolyte contains manganese ions at a concentration of 0.01 to 1 mol / L.

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