A zinc-antimony-iron-cobalt-nickel alloy and its preparation method and application

Abstract

This invention discloses a zinc-antimony-iron-cobalt-nickel alloy, its preparation method, and its applications, belonging to the field of sodium-ion battery materials technology. A pentagonal zinc-antimony-iron-cobalt-nickel alloy is prepared using a simple pulse electrodeposition method, maximizing the utilization of metal ions in the solution. By adjusting the type and concentration of metal ions, pentagonal zinc-antimony-iron-cobalt-nickel alloys with different compositions and components can be prepared. Alternating deposition at different voltages can change the deposition rate of different metal ions while generating more active sites, producing spherical, uniformly packed particles, increasing the specific surface area of ​​the alloy material, which is beneficial for sodium ion insertion and extraction in sodium-ion batteries. When the zinc-antimony-iron-cobalt-nickel pentagonal alloy is used as the negative electrode in a sodium-ion battery, the active metals provide sodium storage capacity, while the inactive metals stabilize the microstructure during sodium ion movement, thereby increasing its cycle stability.

Description

Technical Field

[0001] This invention belongs to the field of sodium-ion battery materials technology, specifically relating to a zinc-antimony-iron-cobalt-nickel alloy, its preparation method, and its application. Background Technology

[0002] Research on sodium-ion batteries and lithium-ion batteries began almost simultaneously in the 1970s, but the successful commercialization of lithium-ion batteries led to a stagnation in sodium-ion battery research. It wasn't until after 2010, with the surge in demand for renewable energy and the urgent need for large-scale energy storage technologies, that sodium-ion batteries experienced another golden age of development. Sodium-ion batteries, with their advantages of high safety, low cost, wide temperature range, and great application potential, are considered the optimal alternative to lithium-ion batteries and are expected to be used in large-scale energy storage devices.

[0003] Sodium-ion batteries operate on a similar principle to lithium-ion batteries, both belonging to the "rocking chair battery" category. They consist of a positive electrode, electrolyte, separator, and negative electrode. Based on the sodium storage mechanism, sodium-ion battery negative electrode materials can be categorized into intercalation reaction materials, conversion reaction materials, and alloy reaction materials. Intercalation reaction materials are primarily carbon-based materials, including graphite, nano-carbon materials, soft carbon, and hard carbon materials. Conversion reaction materials are mainly compounds composed of transition metals and oxygen, sulfur, selenium, and phosphorus. These compounds exhibit certain sodium storage activity when used as negative electrode materials in sodium-ion batteries; the reaction principle involves sodium... + The reaction produces transition metals and corresponding sodium oxide, sodium sulfide, sodium selenide, and sodium phosphide. The alloy reaction materials mainly include non-metallic or metallic elements from Group IV and Group V, which have the ability to form alloys with sodium. Since a single atom can bond with one or more sodium atoms, the alloy reaction materials usually exhibit a large theoretical capacity.

[0004] Alloy reactive materials possess lower operating potentials, which is beneficial for increasing the operating voltage of sodium-ion batteries and thus improving their energy density, making them promising anode materials for sodium-ion batteries. However, similar to conversion reactive materials, alloy reactive materials also suffer from some serious problems, namely poor reaction kinetics and significant volume changes before and after sodium insertion / extraction. This leads to material differentiation and loss of point contact in the current collector, resulting in rapid capacity decay. Therefore, addressing the large volume changes in alloy reactive anode materials is a primary challenge. Multi-element alloys can effectively solve the volume expansion problem of alloy-based anodes, but their preparation mostly involves high-temperature melting or ball milling of various pure metals, resulting in numerous, time-consuming, labor-intensive, and costly preparation steps.

[0005] In the prior art, such as Chinese invention patent CN116876048A, entitled "An Electroplating Solution and Its Application in the Preparation of Copper-Antimony Alloy by Double-Pulse Electrodeposition," a copper-antimony alloy coating is obtained by a double-pulse electrodeposition method. No copper salt needs to be added to the plating solution; copper dissolution and deposition are achieved by applying positive and negative potentials. The dissolved copper ions and antimony ions co-deposit under a negative potential to form an alloy. Another example is Chinese invention patent CN117878303A, entitled "An In-situ Cu-Doped Sb-Zn Alloy Anode Battery Material and Its Preparation Method," which describes an in-situ Cu-doped Sb-Zn alloy anode battery material and its preparation method. Cu originates from the substrate and dissolves in the plating solution under an applied positive voltage, while co-depositing with Sb and Zn at a negative potential to form an Sb-Zn-Cu ternary alloy. For example, CN117878302A, entitled "An Sb-Bi-Cu Alloy Anode Battery Material and Its Preparation Method," describes an Sb-Bi-Cu alloy anode battery material and its preparation method, in which Cu is inactive and originates from the dissolution of the substrate Cu. Summary of the Invention

[0006] 1. Purpose of the invention

[0007] The purpose of this invention is to provide a zinc-antimony-iron-cobalt-nickel alloy, its preparation method, and its applications. This zinc-antimony-iron-cobalt-nickel alloy is prepared using a novel pulsed potential electrodeposition method, employing two consecutive deposition voltages. This effectively simplifies the preparation steps of multi-element alloys. Furthermore, by adjusting the type and mass fraction of metal salts in the solution, multi-element alloys with different compositions can be prepared. When this zinc-antimony-iron-cobalt-nickel alloy is used as a negative electrode material for sodium-ion batteries, during charge and discharge, the zinc and antimony in the alloy exhibit electrochemical activity, providing capacity. While possessing sodium storage capacity, the inactive metals also play a role in stabilizing the structural framework.

[0008] 2. Technical Solution

[0009] To solve the above problems, the technical solution adopted by the present invention is as follows:

[0010] This invention provides a method for preparing a zinc-antimony-iron-cobalt-nickel alloy, which uses a pulsed potential electrodeposition method to prepare the zinc-antimony-iron-cobalt-nickel alloy, specifically including the following steps:

[0011] S1, Prepare solution

[0012] Tartaric acid, citric acid, sodium chloride, and deionized water are mixed to obtain a mixed solution; zinc salt, antimony salt, iron salt, cobalt salt, and nickel salt are added to the above mixed solution, and stirred to dissolve to obtain the final mixed solution;

[0013] in:

[0014] Tartaric acid is a buffer.

[0015] Citric acid acts as a conductive agent and a complexing agent.

[0016] Sodium chloride is used as a conductive agent and to improve the solubility of antimony salts.

[0017] The main salts are zinc salts, antimony salts, iron salts, cobalt salts, and nickel salts;

[0018] S2, pulsed potential electrodeposition

[0019] A zinc-antimony-iron-cobalt-nickel alloy was prepared at 25℃ using copper foil as the cathode and platinum sheet as the anode, by adjusting the pulse potential value and pulse time.

[0020] The pulse potential V1 ranges from -4.0V to -2.0V, and the pulse duration t1 ranges from 2s to 10s.

[0021] The pulse potential V2 is -1.5V to -3.0V, and the pulse time t2 is 1s to 5s. The pulse voltage V2 of this invention is negative. Zinc-antimony-iron-cobalt-nickel alloy continues to be deposited after the pulse voltage V1. The substrate copper foil does not participate in the co-deposition of zinc-antimony-iron-cobalt-nickel alloy, thus ensuring the integrity of the substrate.

[0022] Alternating deposition, with a total deposition time of 120s, can change the deposition rate of different metal ions and generate more active sites, thus producing spherical, uniformly packed particles and increasing the specific surface area of ​​the alloy material.

[0023] Furthermore, in the above-mentioned S1 solution, zinc salt, antimony salt, iron salt, cobalt salt, and nickel salt are added respectively, and another metal salt is added after the added salt has dissolved, which can prevent the precipitation of solids.

[0024] Furthermore, in the final mixed solution prepared in S1 above, the mass concentration of each component is as follows:

[0025] Tartaric acid: 20–80 g / L;

[0026] Citric acid: 20–60 g / L;

[0027] Sodium chloride: 80–120 g / L;

[0028] Zinc salt: 4–8 g / L;

[0029] Antimony salt: 10–14 g / L;

[0030] Iron salts: 4–8 g / L;

[0031] Cobalt salt: 4–8 g / L;

[0032] Nickel salts: 10–14 g / L.

[0033] Furthermore, in the final mixed solution prepared in S1 above, the mass concentration of tartaric acid is 20, 60, or 80 g / L. Even further, in the final mixed solution prepared in S1 above, the mass concentration of tartaric acid is 60 g / L.

[0034] Furthermore, in the final mixed solution prepared in S1 above, the mass concentration of citric acid is 20, 40, or 60 g / L. Even further, in the final mixed solution prepared in S1 above, the mass concentration of citric acid is 20 g / L.

[0035] Furthermore, in the final mixed solution prepared in S1 above, the mass concentration of sodium chloride is 80, 100, or 120 g / L. Even further, in the final mixed solution prepared in S1 above, the mass concentration of sodium chloride is 100 g / L.

[0036] Furthermore, in the final mixed solution prepared in S1 above, the mass concentration of the zinc salt is 4, 6, or 8 g / L. Even further, in the final mixed solution prepared in S1 above, the mass concentration of the zinc salt is 4 g / L.

[0037] Furthermore, in the final mixed solution prepared in S1 above, the mass concentration of antimony salt is 10, 12, or 14 g / L. Even further, in the final mixed solution prepared in S1 above, the mass concentration of antimony salt is 12 g / L.

[0038] Furthermore, in the final mixed solution prepared in S1 above, the mass concentration of the iron salt is 4, 6, or 8 g / L. Even further, in the final mixed solution prepared in S1 above, the mass concentration of the iron salt is 4 g / L.

[0039] Furthermore, in the final mixed solution prepared in S1 above, the mass concentration of the cobalt salt is 4, 6, or 8 g / L. Even further, in the final mixed solution prepared in S1 above, the mass concentration of the cobalt salt is 6 g / L.

[0040] Furthermore, in the final mixed solution prepared in S1 above, the mass concentration of the nickel salt is 10, 12, or 14 g / L. Even further, in the final mixed solution prepared in S1 above, the mass concentration of the nickel salt is 12 g / L.

[0041] Furthermore, in the final mixed solution prepared in S1 above, the mass concentration of each component is as follows:

[0042] Tartaric acid: 60 g / L;

[0043] Citric acid: 20g / L;

[0044] Sodium chloride: 100g / L;

[0045] Zinc salt: 4g / L;

[0046] Antimony salt: 12 g / L;

[0047] Iron salts: 4g / L;

[0048] Cobalt salt: 6 g / L;

[0049] Nickel salt: 12g / L.

[0050] Furthermore, the aforementioned zinc salts, iron salts, cobalt salts, and nickel salts include sulfates and / or chlorides. Even further, the aforementioned zinc salts, iron salts, cobalt salts, and nickel salts include chlorides.

[0051] Furthermore, the aforementioned antimony salts include potassium antimony tartrate or antimony chloride. Even further, the aforementioned antimony salts include antimony chloride.

[0052] Furthermore, in S2 above, the pulse potential V1 is -2.7V to -2.3V. Even further, in S2 above, the pulse potential V1 is -2.7V, -2.5V, or -2.3V.

[0053] Furthermore, in S2 above, the pulse time t1 is 2s or 10s.

[0054] Furthermore, in S2 above, the pulse potential V2 is -2.0V.

[0055] Furthermore, in S2 above, the pulse time t2 is 1s or 5s.

[0056] The present invention also provides a zinc-antimony-iron-cobalt-nickel alloy prepared by the above-mentioned method for preparing zinc-antimony-iron-cobalt-nickel alloy.

[0057] The present invention also provides the application of the above-mentioned zinc-antimony-iron-cobalt-nickel alloy in the preparation of sodium-ion batteries, wherein the above-mentioned zinc-antimony-iron-cobalt-nickel alloy is used as the negative electrode material.

[0058] The present invention also provides a sodium-ion battery comprising the above-mentioned zinc-antimony-iron-cobalt-nickel alloy, wherein the zinc-antimony-iron-cobalt-nickel alloy is the negative electrode material.

[0059] 3. Beneficial effects

[0060] Compared with the prior art, the advantages of this invention are as follows:

[0061] (1) The present invention provides a zinc-antimony-iron-cobalt-nickel alloy and its preparation method and application. A zinc-antimony-iron-cobalt-nickel pentagonal alloy is prepared by a simple pulse potential electrodeposition method, which eliminates the cumbersome preparation process of traditional multi-element alloys and the steps of mixing it with binder and conductive agent as the negative electrode of sodium-ion battery. In addition to inexpensive buffer, conductive agent, complexing agent and sodium chloride, there are only metal salts in the solution, and the overall solution cost is low. The preparation method can maximize the use of metal ions in the mixed solution. By adjusting the type and concentration of metal ions, zinc-antimony-iron-cobalt-nickel pentagonal alloys with different compositions and components can be prepared.

[0062] (2) The present invention provides a zinc-antimony-iron-cobalt-nickel alloy and its preparation method and application. The alternating deposition of different voltages can change the deposition rate of different metal ions and generate more active sites, prepare spherical uniformly stacked particles, increase the specific surface area of ​​the zinc-antimony-iron-cobalt-nickel alloy material, and facilitate the insertion and extraction of sodium ions in sodium-ion batteries.

[0063] (3) The present invention provides a zinc-antimony-iron-cobalt-nickel alloy, its preparation method, and its application. The pulse voltage V2 is negative, and the zinc-antimony-iron-cobalt-nickel alloy continues to be deposited after the pulse voltage V1. The substrate copper foil does not participate in the co-deposition of the zinc-antimony-iron-cobalt-nickel alloy, ensuring the integrity of the substrate. Specifically, during the co-deposition process, metal ions such as zinc, antimony, iron, cobalt, and nickel in the solution migrate towards the cathode (i.e., the substrate copper foil) under the action of an electric field, gain electrons on its surface, and are reduced to form a dense alloy coating. However, if the substrate copper foil participates in this reaction, it will not only lead to the consumption of copper foil, affecting the thickness and conductivity of the substrate, but may also introduce impurity elements, disrupting the composition ratio and performance of the coating. This deposition method ensures the integrity of the substrate copper foil, allowing it to act only as a conductive medium and substrate throughout the electroplating process without altering its physical and chemical properties.

[0064] (4) The present invention provides a zinc-antimony-iron-cobalt-nickel alloy and its preparation method and application. When the zinc-antimony-iron-cobalt-nickel pentagonal alloy is used as the negative electrode of a sodium-ion battery, the active metal provides sodium storage capacity, and the inactive metal stabilizes the microstructure during the movement of sodium ions to increase its cycle stability. Attached Figure Description

[0065] Figure 1 This is a pulse voltage-time diagram for preparing zinc-antimony-iron-cobalt-nickel alloys.

[0066] Figure 2 This is a SEM image of the zinc-antimony-iron-cobalt-nickel alloy prepared in Example 2.

[0067] Figure 3 This is a SEM image of the zinc-antimony-iron-cobalt-nickel alloy prepared in Comparative Example 2.

[0068] Figure 4These are electrochemical performance graphs of the zinc-antimony-iron-cobalt-nickel alloys prepared in Example 2 and Comparative Example 2. Detailed Implementation

[0069] The present invention will be further described below with reference to specific embodiments.

[0070] It should be noted that terms such as "upper", "lower", "left", "right", and "middle" used in this specification are only for clarity of description and are not intended to limit the scope of implementation. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of implementation of this invention.

[0071] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains; the term “and / or” as used herein includes any and all combinations of one or more of the associated listed items.

[0072] Unless otherwise specified in the examples, the procedures should be performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0073] As used herein, the term “about” is used to provide for the flexibility and imprecision associated with a given term, measure, or value. Those skilled in the art can readily determine the degree of flexibility for a particular variable.

[0074] As used herein, the term “at least one of…” is intended to be synonymous with “one or more of…”. For example, “at least one of A, B, and C” explicitly includes only A, only B, only C, and combinations thereof.

[0075] Concentration, amount, and other numerical data may be presented in range format herein. It should be understood that such range format is used solely for convenience and brevity and should be flexibly interpreted to include not only the values ​​explicitly stated as the limits of the range, but also all individual values ​​or subranges encompassed within the range, as if each value and subrange were explicitly stated. For example, a range of values ​​from about 1 to about 4.5 should be interpreted to include not only the explicitly stated limits of 1 to 4.5, but also individual numbers (such as 2, 3, 4) and subranges (such as 1 to 3, 2 to 4, etc.). The same principle applies to ranges that describe only a single value, such as “less than about 4.5,” which should be interpreted to include all the aforementioned values ​​and ranges. Furthermore, this interpretation should apply regardless of the breadth of the range or characteristic described.

[0076] Example 1

[0077] This embodiment provides a method for preparing a zinc-antimony-iron-cobalt-nickel alloy and the prepared zinc-antimony-iron-cobalt-nickel alloy.

[0078] The preparation method of zinc-antimony-iron-cobalt-nickel alloy includes the following steps:

[0079] S1, Prepare solution

[0080] Dissolve 60g tartaric acid, 40g citric acid, 80g sodium chloride, and deionized water.

[0081] Add 8g zinc chloride, 10g antimony chloride, 8g ferric chloride, 6g cobalt chloride, and 14g nickel chloride in sequence;

[0082] Add the remaining deionized water and bring the volume to 1L to obtain the solution.

[0083] S2, pulsed potential electrodeposition

[0084] At 25℃, using copper foil as the cathode and platinum sheet as the anode, with pulse potential V1 of -2.5V and pulse time t1 of 10s, pulse potential V2 of -2.0V and pulse time t2 of 5s, alternating deposition was performed for a total deposition time of 120s. Figure 1 As shown, a zinc-antimony-iron-cobalt-nickel alloy was obtained after pulsed potential electrodeposition.

[0085] Example 2

[0086] This embodiment provides a method for preparing a zinc-antimony-iron-cobalt-nickel alloy and the prepared zinc-antimony-iron-cobalt-nickel alloy.

[0087] The preparation method of zinc-antimony-iron-cobalt-nickel alloy includes the following steps:

[0088] S1, Prepare solution

[0089] Dissolve 60g tartaric acid, 20g citric acid, 100g sodium chloride, and deionized water.

[0090] Add 4g zinc chloride, 12g antimony chloride, 4g ferric chloride, 6g cobalt chloride, and 12g nickel chloride in sequence;

[0091] Add the remaining deionized water and bring the volume to 1L to obtain the solution.

[0092] S2, pulsed potential electrodeposition

[0093] At 25℃, copper foil was used as the cathode and platinum sheet as the anode. The pulse potential V1 was -2.5V and the pulse time t1 was 10s. The pulse potential V2 was -2.0V and the pulse time t2 was 5s. The alternating deposition was carried out for a total deposition time of 120s. Zinc-antimony-iron-cobalt-nickel alloy was obtained after pulse potential electrodeposition.

[0094] Figure 2This is a SEM image of the zinc-antimony-iron-cobalt-nickel alloy prepared in this embodiment. It can be seen that the prepared spherical uniformly packed particles increase the specific surface area of ​​the alloy material, which is beneficial for the insertion and extraction of sodium ions in sodium-ion batteries.

[0095] Example 3

[0096] This embodiment provides a method for preparing a zinc-antimony-iron-cobalt-nickel alloy and the prepared zinc-antimony-iron-cobalt-nickel alloy.

[0097] The preparation method of zinc-antimony-iron-cobalt-nickel alloy includes the following steps:

[0098] S1, Prepare solution

[0099] Dissolve 80g tartaric acid, 40g citric acid, 120g sodium chloride and deionized water.

[0100] Add 6g zinc chloride, 10g antimony chloride, 6g ferric chloride, 8g cobalt chloride, and 12g nickel chloride in sequence;

[0101] Add the remaining deionized water and bring the volume to 1L to obtain the solution.

[0102] S2, pulsed potential electrodeposition

[0103] At 25℃, copper foil was used as the cathode and platinum sheet as the anode. The pulse potential V1 was -2.5V and the pulse time t1 was 10s. The pulse potential V2 was -2.0V and the pulse time t2 was 5s. The alternating deposition was carried out for a total deposition time of 120s. Zinc-antimony-iron-cobalt-nickel alloy was obtained after pulse potential electrodeposition.

[0104] Example 4

[0105] This embodiment provides a method for preparing a zinc-antimony-iron-cobalt-nickel alloy and the prepared zinc-antimony-iron-cobalt-nickel alloy.

[0106] The preparation method of zinc-antimony-iron-cobalt-nickel alloy includes the following steps:

[0107] S1, Prepare solution

[0108] Dissolve 60g tartaric acid, 60g citric acid, 100g sodium chloride, and deionized water.

[0109] Add 8g zinc chloride, 12g antimony chloride, 4g ferric chloride, 6g cobalt chloride, and 10g nickel chloride in sequence;

[0110] Add the remaining deionized water and bring the volume to 1L to obtain the solution.

[0111] S2, pulsed potential electrodeposition

[0112] At 25℃, copper foil was used as the cathode and platinum sheet as the anode. The pulse potential V1 was -2.7V and the pulse time t1 was 10s. The pulse potential V2 was -2.0V and the pulse time t2 was 5s. The alternating deposition was carried out for a total deposition time of 120s. Zinc-antimony-iron-cobalt-nickel alloy was obtained after pulse potential electrodeposition.

[0113] Example 5

[0114] This embodiment provides a method for preparing a zinc-antimony-iron-cobalt-nickel alloy and the prepared zinc-antimony-iron-cobalt-nickel alloy.

[0115] The preparation method of zinc-antimony-iron-cobalt-nickel alloy includes the following steps:

[0116] S1, Prepare solution

[0117] Dissolve 20g tartaric acid, 40g citric acid, 120g sodium chloride and deionized water.

[0118] Add 6g zinc chloride, 14g antimony chloride, 6g ferric chloride, 4g cobalt chloride, and 12g nickel chloride in sequence;

[0119] Add the remaining deionized water and bring the volume to 1L to obtain the solution.

[0120] S2, pulsed potential electrodeposition

[0121] At 25℃, copper foil was used as the cathode and platinum sheet as the anode. The pulse potential V1 was -2.3V and the pulse time t1 was 10s. The pulse potential V2 was -2.0V and the pulse time t2 was 5s. The alternating deposition was carried out for a total deposition time of 120s. Zinc-antimony-iron-cobalt-nickel alloy was obtained after pulse potential electrodeposition.

[0122] Example 6

[0123] This embodiment provides a method for preparing a zinc-antimony-iron-cobalt-nickel alloy and the prepared zinc-antimony-iron-cobalt-nickel alloy.

[0124] The preparation method of zinc, antimony, iron, cobalt, and nickel includes the following steps:

[0125] S1, Prepare solution

[0126] Dissolve 60g tartaric acid, 20g citric acid, 100g sodium chloride, and deionized water.

[0127] Add 8g zinc chloride, 12g antimony chloride, 8g ferric chloride, 6g cobalt chloride, and 10g nickel chloride in sequence;

[0128] Add the remaining deionized water and bring the volume to 1L to obtain the solution.

[0129] S2, pulsed potential electrodeposition

[0130] At 25℃, copper foil was used as the cathode and platinum sheet as the anode. The pulse potential V1 was -2.5V and the pulse time t1 was 2s. The pulse potential V2 was -2.0V and the pulse time t2 was 1s. The alternating deposition was carried out for a total deposition time of 120s. Zinc-antimony-iron-cobalt-nickel alloy was obtained after pulse potential electrodeposition.

[0131] Comparative Example 1

[0132] This embodiment provides a method for preparing a zinc-antimony-iron-cobalt-nickel alloy and the prepared zinc-antimony-iron-cobalt-nickel alloy.

[0133] The preparation method of zinc-antimony-iron-cobalt-nickel alloy includes the following steps:

[0134] Dissolve 60g tartaric acid, 20g citric acid, 100g sodium chloride, and deionized water.

[0135] Add 4g zinc chloride, 12g antimony chloride, 4g ferric chloride, 6g cobalt chloride, and 12g nickel chloride in sequence;

[0136] Add the remaining deionized water and bring the volume to 1L to obtain the solution.

[0137] A zinc-antimony-iron-cobalt-nickel alloy was obtained by direct deposition at a constant potential of -2.5V for 120s.

[0138] Comparative Example 2

[0139] This embodiment provides a method for preparing a zinc-antimony-iron-cobalt-nickel alloy and the prepared zinc-antimony-iron-cobalt-nickel alloy.

[0140] The preparation method of zinc-antimony-iron-cobalt-nickel alloy includes the following steps:

[0141] S1, Prepare solution

[0142] Dissolve 60g tartaric acid, 20g citric acid, 100g sodium chloride, and deionized water.

[0143] Add 4g zinc chloride, 12g antimony chloride, 4g ferric chloride, 6g cobalt chloride, and 12g nickel chloride in sequence;

[0144] Add the remaining deionized water and bring the volume to 1L to obtain the solution.

[0145] S2, pulsed potential electrodeposition

[0146] The pulse potential V1 is -2.5V, the pulse time is t1 and it is 1s, the pulse potential V2 is -2.0V, the pulse time is t2 and it is 500ms, and the deposition is carried out alternately, with a total deposition time of 120s.

[0147] Results analysis:

[0148] Figure 3This is a SEM image of the zinc-antimony-iron-cobalt-nickel alloy prepared in this comparative example. It can be seen that 1s and 500ms pulse times can produce sand-like particles. These particles have a small specific surface area, which affects the insertion of sodium ions into the particles, causing sodium ions to accumulate on the alloy surface and resulting in poor electrochemical performance.

[0149] Figure 4 The graphs show the electrochemical performance of the zinc-antimony-iron-cobalt-nickel alloys prepared in Example 2 and Comparative Example 2. The discharge specific capacity of the zinc-antimony-iron-cobalt-nickel alloy anode in Comparative Example 2 drops sharply in the first 30 cycles, then decreases steadily after 30 cycles, and drops from 432.71 mAh / g to 160 mAh / g after 100 cycles. In contrast, the zinc-antimony-iron-cobalt-nickel alloy anode prepared in Example 2 still has a discharge specific capacity of 370 mAh / g after 190 cycles. This indicates that changing the pulse time to t1 and t2 affects the electrochemical performance of the alloy anode.

[0150] Example 7

[0151] This embodiment provides the application of the zinc-antimony-iron-cobalt-nickel alloy in Examples 1-6 and Comparative Examples 1-2, for use as a negative electrode material in sodium-ion batteries.

[0152] The zinc-antimony-iron-cobalt-nickel alloys obtained in Examples 1-6 and Comparative Examples 1-2 were used as anode materials for sodium-ion batteries and assembled into coin cells. Electrochemical performance tests were conducted on a Newway battery tester to determine the discharge specific capacity and coulombic efficiency. The test results are shown in Table 1. As can be seen from Table 1, the zinc-antimony-iron-cobalt-nickel alloys obtained in this application, as anode materials for sodium-ion batteries, have high specific capacity, excellent cycle performance and rate performance, and exhibit good electrochemical performance.

[0153] Table 1

[0154]

[0155] The zinc-antimony-iron-cobalt-nickel alloy of this invention is not limited to sodium-ion battery materials, but can also be used in other battery materials.

[0156] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the present invention in any way. Other variations and modifications are possible without departing from the technical solutions described in the claims.

Claims

1. A method for preparing a zinc-antimony-iron-cobalt-nickel alloy, characterized in that, The method includes the following steps: S1, Prepare solution Tartaric acid, citric acid, sodium chloride, and deionized water are mixed to obtain a mixed solution; zinc salt, antimony salt, iron salt, cobalt salt, and nickel salt are added to the mixed solution and stirred to dissolve, thus obtaining the final mixed solution; S2, pulsed potential electrodeposition At 25℃, using copper foil as the cathode and platinum sheet as the anode, The pulse potential V1 ranges from -4.0V to -2.0V, and the pulse duration t1 ranges from 2s to 10s. The pulse potential V2 ranges from -1.5V to -3.0V, and the pulse duration t2 ranges from 1s to 5s. Alternating deposition, with a total deposition time of 120s.

2. The method for preparing a zinc-antimony-iron-cobalt-nickel alloy according to claim 1, characterized in that, The zinc, iron, cobalt, and nickel salts include sulfates and / or chlorides; and / or The antimony salt includes potassium antimony tartrate or antimony chloride.

3. The method for preparing a zinc-antimony-iron-cobalt-nickel alloy according to claim 2, characterized in that, The zinc salts, antimony salts, iron salts, cobalt salts, and nickel salts include chloride salts.

4. The method for preparing a zinc-antimony-iron-cobalt-nickel alloy according to claim 3, characterized in that, The mass concentrations of each component in the solution prepared in S1 are as follows: Tartaric acid: 20–80 g / L; Citric acid: 20–60 g / L; Sodium chloride: 80–120 g / L; Zinc salt: 4–8 g / L; Antimony salt: 10–14 g / L; Iron salts: 4–8 g / L; Cobalt salt: 4–8 g / L; Nickel salts: 10–14 g / L.

5. The method for preparing a zinc-antimony-iron-cobalt-nickel alloy according to claim 4, characterized in that, The tartaric acid has a mass concentration of 20, 60, or 80 g / L; and / or The citric acid has a mass concentration of 20, 40, or 60 g / L; and / or The sodium chloride concentration is 80, 100, or 120 g / L; and / or The zinc salt has a mass concentration of 4, 6, or 8 g / L; and / or The antimony salt has a mass concentration of 10, 12, or 14 g / L; and / or The iron salt has a mass concentration of 4, 6, or 8 g / L; and / or The cobalt salt has a mass concentration of 4, 6, or 8 g / L; and / or The mass concentration of the nickel salt is 10, 12 or 14 g / L.

6. A method for preparing a zinc-antimony-iron-cobalt-nickel alloy according to any one of claims 1-5, characterized in that, In S2, the pulse potential V1 is -2.7V to -2.3V.

7. The method for preparing a zinc-antimony-iron-cobalt-nickel alloy according to claim 6, characterized in that, The pulse potential V1 is -2.7V, -2.5V, or -2.3V; the pulse duration t1 is 2s or 10s; and / or The pulse potential V2 is -2.0V; the pulse duration t2 is 1s or 5s.

8. The zinc-antimony-iron-cobalt-nickel alloy prepared by any one of the zinc-antimony-iron-cobalt-nickel alloy preparation methods according to any one of claims 1-7.

9. The application of the zinc-antimony-iron-cobalt-nickel alloy according to claim 8 in the preparation of sodium-ion batteries, characterized in that, The zinc-antimony-iron-cobalt-nickel alloy is used as the negative electrode material.

10. A sodium-ion battery, characterized in that, The sodium-ion battery includes the zinc-antimony-iron-cobalt-nickel alloy of claim 8, wherein the zinc-antimony-iron-cobalt-nickel alloy is the negative electrode material.

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