CN113363411B - Positive electrode for nickel-hydrogen secondary battery, preparation method of positive electrode and nickel-hydrogen secondary battery - Google Patents
Positive electrode for nickel-hydrogen secondary battery, preparation method of positive electrode and nickel-hydrogen secondary battery Download PDFInfo
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Abstract
The invention provides a positive electrode for a nickel-hydrogen secondary battery, which comprises a positive electrode substrate and a phosphorus-doped nickel-cobalt mixed positive electrode material layer compounded on the surface of the positive electrode substrate. The introduction of cobalt can increase Ni (OH)2The overall conductivity of the material is improved, so that the utilization rate of the electrode material is improved; has certain inhibiting effect on the formation of gamma-NiOOH, thereby obviously improving the stability of the electrode material. Besides promoting the improvement of the conductivity and stability of the electrode material, the introduction of P has a certain promotion effect on the improvement of the discharge voltage and the specific capacity due to the synergy and promotion effect among the three elements of Ni, Co and P.
Description
Technical Field
The invention belongs to the technical field of novel electrochemical energy storage, and particularly relates to a positive electrode for a nickel-metal hydride secondary battery, a preparation method of the positive electrode and the nickel-metal hydride secondary battery.
Background
With the exhaustion of fossil fuels and the increasing increase of environmental pollution, the development of clean renewable energy is crucial to the protection of ecological environment. The key problem of the wide application of renewable energy sources such as solar energy, wind energy and the like is that the clean energy sources have intermittency and imbalance in time and space, so that the clean energy sources cannot be directly incorporated into a power grid to be supplied to people for use, and the clean energy sources must be assisted by a certain energy storage device for use. Therefore, it is important for large-scale storage of energy. Electrochemical energy storage systems, particularly batteries, are currently considered to be one of the most widely and promising energy storage technologies. The batteries which have been successfully commercialized at present mainly include four types, namely lithium ion batteries, lead-acid batteries, flow batteries and high-temperature sodium-sulfur batteries. The four batteries are not universal and have certain limitations in practical large-scale energy storage applications. The lithium ion battery has higher cost and certain danger due to the use of organic electrolyte; the lead-acid battery has low energy density and short cycle life; the flow battery has high cost, low energy density and difficult maintenance; the sodium-sulfur battery is usually operated at the high temperature of 300-350 ℃, and the thermal corrosion brings great potential safety hazard.
Therefore, it is important to develop a secondary battery which is more stable, safer, and suitable for large-scale energy storage. Hydrogen (H)2) Widely available in the universe, has high specific energy (three times that of traditional gasoline) and is generally considered as a potential green energy source. In addition, the overpotential for electrochemical conversion based on Hydrogen Evolution Reaction (HER) and Hydrogen Oxidation Reaction (HOR) is 0V, which means H2The electrode has fast dynamics and stable cycle performance, and is matched with the requirement of large-scale energy storage. Thus, various H2Batteries have attracted more attention in laboratory research and commercial applications. As regards hydrogen cells, the earliest trace was to the nickel-metal hydride cells of the United states department of aerospace (NASA), which cells were made of Ni (OH)2The anode and the Pt/C catalyst cathode are formed, the electrolyte is KOH solution, and the electrode reaction during discharging is as follows:
and (3) positive electrode: 2NiOOH +2H2O+2e-→2Ni(OH)2+2OH-E＝0.52V vs SHE
Negative electrode: h2+2OH-→2H2O+2e-E＝-0.83V vs SHE
All-battery: 2NiOOH + H2→2Ni(OH)2E＝1.35V
The nickel-metal hydride battery of NASA has the following advantages: long cycle life (>5000 times), high durability under harsh conditions (e.g., below zero temperature), with the potential for large-scale applications. However, the high cost of the anode catalyst and the Ni (OH)2The development of the nickel-metal hydride battery is limited by the problems of poor conductivity of the anode, slow dynamics in the charging and discharging process, unstable structure and the like. Thus, development of a less expensive HER/HOR bifunctional catalyst and improvement of Ni (OH)2The problem of the positive electrode is particularly necessary.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a positive electrode for a nickel-metal hydride secondary battery, a method for preparing the same, and a nickel-metal hydride secondary battery, wherein the positive electrode for a nickel-metal hydride secondary battery provided by the present invention has a high discharge platform and specific capacity, an excellent rate capability, an excellent cycle life, and almost no significant attenuation of capacity up to 5000 cycles.
The invention provides a positive electrode for a nickel-hydrogen secondary battery, which comprises a positive electrode substrate and a phosphorus-doped nickel-cobalt mixed positive electrode material layer compounded on the surface of the positive electrode substrate.
Preferably, the positive electrode substrate is selected from a carbon material substrate or a metal substrate;
the carbon material substrate is carbon cloth, carbon paper, carbon felt, graphite felt, carbon micron and nano fiber, and at least one of modified carbon cloth, carbon paper, carbon felt, graphite felt, carbon micron and nano fiber;
the metal substrate is foamed nickel, foamed copper, nickel foil, copper foil, titanium foil or titanium mesh.
The invention also provides a preparation method of the anode, which comprises the following steps:
and depositing a phosphorus-doped nickel-cobalt mixed positive electrode material layer on the surface of the positive electrode substrate by a dynamic electrochemical deposition method to obtain the positive electrode for the nickel-hydrogen secondary battery.
Preferably, in the electrolyte, the concentration of cobalt nitrate is 0.001-10 mol/L, the concentration of nickel nitrate is 0.001-10 mol/L, and the concentration of sodium hypophosphite is 0.001-2 mol/L.
Preferably, the voltage deposited in the dynamic electrochemical deposition method is-1.2V to 0.2V.
Preferably, the number of deposition turns in the dynamic electrochemical deposition method is 5-50.
Preferably, the deposition is carried out in a three-electrode system in the dynamic electrochemical deposition method, wherein the working electrode is a positive electrode substrate, the reference electrode is Ag/AgCl, and the counter electrode is a platinum sheet.
The invention also provides a nickel-hydrogen secondary battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode is selected from the positive electrode for the nickel-hydrogen secondary battery.
Preferably, the negative electrode is a current collector loaded with a catalyst, and the catalyst is selected from one or more of non-noble metals, noble metals and carbon materials;
preferably, the non-noble metal catalyst comprises Ni, NiN, NiS, NiP, NiPS, NiMo, NiCoMo, MoO2、MoS2、MoC、MoC2、MoP、WO2、WS2、WC、WC2And WP; the noble metal catalyst comprises one or more of Pt, Pd, Ir and Ru; the carbon material comprises one of a micro-or nanoparticle, a micro-or nanosphere, a micro-or nanowire, a micro-or nanosheet, or a micro-or nanotube structure;
the electrolyte is a strong alkali aqueous solution; the concentration of strong base in the electrolyte is 0.01-10 mol/L;
the separator is selected from water-based battery separators.
Preferably, the hydrogen pressure inside the secondary battery negative electrode is 1 to 100 atm;
the structure of the secondary battery includes a button type battery or a cylindrical type battery.
Compared with the prior art, the invention provides a positive electrode for a nickel-hydrogen secondary battery, which comprises a positive electrode substrate and a phosphorus-doped nickel-cobalt mixed positive electrode material layer compounded on the surface of the positive electrode substrate. The introduction of cobalt can increase Ni (OH)2The overall conductivity of the material is improved, so that the utilization rate of the electrode material is improved; has certain inhibiting effect on the formation of gamma-NiOOH, thereby obviously improving the stability of the electrode material. Besides the promotion effect on the improvement of the conductivity and stability of the electrode material, the introduction of P has a certain promotion effect on the improvement of the discharge voltage and the specific capacity through the synergy and promotion effect among the three elements of Ni, Co and P.
The nickel-hydrogen secondary battery provided by the invention solves the problems of the traditional Ni (OH)2The conductivity of the anode is poor, the dynamics in the charging and discharging process is slow, the structure is unstable, and the rate capability is obviously improved; compared with Ni-Co hydrogen batteries which are not doped with P, the Ni-Co hydrogen batteries have higher discharge platforms and higher specific capacities, and have more advantages for future commercialization.
The result shows that the anode for the nickel-hydrogen secondary battery provided by the invention has higher discharge platform and specific capacity, excellent rate performance and excellent cycle life, and almost no obvious capacity attenuation can reach 5000 circles.
Drawings
Fig. 1 is a photograph showing the appearance of an aqueous phosphorus-doped nickel-cobalt-hydrogen secondary battery according to the present invention;
FIG. 2 is a current-voltage curve of the positive electrode for a nickel-hydrogen secondary battery according to the present invention during deposition;
FIG. 3 is a Scanning Electron Microscope (SEM) image of a positive electrode for a nickel-hydrogen secondary battery provided by the invention;
FIG. 4 is a three-electrode electrochemical impedance test result curve of the positive electrode for the nickel-hydrogen secondary battery prepared in example 5 of the present invention in an alkaline KOH electrolyte;
fig. 5 is a graph showing the result of cyclic voltammetry tests on an alkaline KOH electrolyte for a nickel-hydrogen secondary battery prepared in example 6 of the present invention;
fig. 6 is a charge-discharge test result curve of the nickel-hydrogen secondary battery prepared in example 7 of the present invention in an alkaline KOH electrolyte;
fig. 7 is a result curve of the rate capability cycle performance test of the nickel-hydrogen secondary battery prepared in example 8 of the present invention in the alkaline KOH electrolyte.
Detailed Description
The invention provides a positive electrode for a nickel-hydrogen secondary battery, which comprises a positive electrode substrate and a phosphorus-doped nickel-cobalt mixed positive electrode material layer compounded on the surface of the positive electrode substrate.
The positive electrode for the nickel-hydrogen secondary battery comprises a positive electrode substrate, wherein the positive electrode substrate is selected from a carbon material substrate or a metal substrate;
the carbon material substrate is carbon cloth, carbon paper, carbon felt, graphite felt, carbon micron and nanofiber, and at least one of the carbon cloth, the carbon paper, the carbon felt, the graphite felt, the carbon micron and the nanofiber which are modified; wherein the modification is a heteroatom modification other than carbon.
The metal substrate is foamed nickel, foamed copper, nickel foil, copper foil, titanium foil or titanium mesh.
The positive electrode for the nickel-metal hydride secondary battery also comprises a phosphorus-doped nickel-cobalt mixed positive electrode material layer compounded on the surface of the positive electrode substrate.
The phosphorus-doped nickel-cobalt mixed positive electrode material has a 3D nanosheet or nanoflower shape.
Wherein, the introduction of cobalt can increase Ni (OH)2The overall conductivity of the material is improved, so that the utilization rate of the electrode material is improved; has certain inhibiting effect on the formation of gamma-NiOOH, thereby obviously improving the stability of the electrode material. Besides the promotion effect on the improvement of the conductivity and stability of the electrode material, the introduction of P has a certain promotion effect on the improvement of the discharge voltage and the specific capacity through the synergy and promotion effect among the three elements of Ni, Co and P.
The invention also provides a preparation method of the positive electrode for the nickel-hydrogen secondary battery, which comprises the following steps:
and depositing a phosphorus-doped nickel-cobalt mixed positive electrode material layer on the surface of the positive electrode substrate by a dynamic electrochemical deposition method to obtain the positive electrode for the nickel-hydrogen secondary battery.
The invention adopts a dynamic electrochemical deposition method, namely a cyclic voltammetry method to prepare the anode. Wherein, cobalt nitrate, nickel nitrate and sodium hypophosphite form a mixed solution as an electrolyte. In the electrolyte, the concentration of the cobalt nitrate is 0.001mol/L to 10mol/L, preferably 0.001mol/L, 0.01mol/L, 0.1mol/L, 0.5mol/L, 1.0mol/L, 5mol/L, 10mol/L, or any value between 0.001mol/L and 10 mol/L.
The concentration of nickel nitrate is 0.001mol/L to 10mol/L, preferably 0.001mol/L, 0.01mol/L, 0.1mol/L, 0.5mol/L, 1.0mol/L, 5mol/L, 10mol/L, or any value between 0.001mol/L to 10 mol/L.
The concentration of sodium hypophosphite is 0.001-2 mol/L, preferably 0.001-0.01 mol/L, 0.1mol/L, 0.5mol/L, 1.0mol/L, 2.0mol/L, or any value between 0.001-2 mol/L.
In some embodiments of the invention, the electrolyte comprises 0.1mol/L cobalt nitrate, 0.1mol/L nickel nitrate and 0.05mol/L sodium hypophosphite.
The dynamic electrochemical deposition method is carried out in a three-electrode system, wherein the working electrode is a positive electrode substrate, the reference electrode is Ag/AgCl, and the counter electrode is a platinum sheet.
The specific selection of the positive electrode substrate is referred to above, and is not described herein.
The voltage for deposition is-1.2V-0.2V. The number of deposited circles in the dynamic electrochemical deposition method is 5-50 circles, preferably 10 circles, 20 circles or 25 circles. The volume of deposition can be controlled by the number of passes of the deposition.
Compared with the constant-voltage deposition and constant-current deposition methods, the dynamic electrochemical deposition method provided by the invention can obtain electrode plates which are more uniform and stably combined with the substrate.
The invention also provides a nickel-hydrogen secondary battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte. The nickel-hydrogen secondary battery provided by the invention is a water-system phosphorus-doped nickel-cobalt-hydrogen secondary battery.
Referring to fig. 1, fig. 1 is a photograph showing the appearance of the aqueous phosphorus-doped nickel-cobalt-hydrogen secondary battery according to the present invention.
The positive electrode is selected from the positive electrodes for nickel-metal hydride secondary batteries. The redox reaction between hydroxide and oxyhydroxide of nickel and cobalt elements in different valence states is carried out at the interface of the electrolyte.
Wherein, transition metal element ions in the anode are nickel and cobalt; the redox reaction of the transition metal between different valence states is the redox reaction of nickel between different valence states under an alkaline condition, and the redox reaction of cobalt between different valence states under the alkaline condition. Furthermore, the nickel has different valence states of NiO and Ni (OH)2Or NiOOH, the different valence states of the cobalt are CoO and Co2O3、Co(OH)2Or CoOOH.
The negative electrode is a current collector loaded with a catalyst. The current collector is a carrier that carries the catalyst. The negative electrode is used for carrying out oxidation-reduction reaction of HER/HOR conversion at the interface of the negative electrode and the electrolyte. In the present invention, the catalyst is selected from one or more of non-noble metals, noble metals and carbon materials; preferably, the non-noble metal catalyst comprises Ni, NiN, NiS, NiP, NiPS, NiMo, NiCoMo, MoO2、MoS2、MoC、MoC2、MoP、WO2、WS2、WC、WC2And WP; the noble metal catalyst comprises one or more of Pt, Pd, Ir and Ru; the carbon material comprises one of a micro-or nanoparticle, a micro-or nanosphere, a micro-or nanowire, a micro-or nanosheet, or a micro-or nanotube structure; the catalyst is selected from non-noble metals, carbon materials, mixtures of non-noble metals and nanocarbon and mixtures of noble metals and nanocarbon.
The electrolyte is strong alkali aqueous solution, preferably KOH and NaOH, and more preferably KOH; the concentration of the strong base in the electrolyte is 0.01-10 mol/L, preferably 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.5mol/L, 1.0mol/L, 5.0mol/L, 10mol/L, or any value between 0.01-10 mol/L. Compared with the traditional lithium ion battery adopting the organic electrolyte, the aqueous alkaline electrolyte in the nickel-hydrogen secondary battery provided by the invention is less prone to spontaneous combustion in actual use and has higher safety.
The diaphragm is arranged between the positive electrode and the negative electrode and used for separating the positive electrode from the negative electrode, and the diaphragm is selected from water-based battery diaphragms.
In the present invention, the hydrogen pressure inside the secondary battery negative electrode is 1 to 100atm, preferably 1atm, 5atm, 10atm, 50atm, 100atm, or any value between 1 to 100 atm.
The structure of the secondary battery includes a button type battery or a cylindrical type battery.
The introduction of cobalt can increase Ni (OH)2The conductivity of the whole material is improved, so that the utilization rate of the electrode material is improved; has certain inhibiting effect on the formation of gamma-NiOOH, thereby obviously improving the stability of the electrode material. Besides the promotion effect on the improvement of the conductivity and stability of the electrode material, the introduction of P has a certain promotion effect on the improvement of the discharge voltage and the specific capacity through the synergy and promotion effect among the three elements of Ni, Co and P.
The nickel-hydrogen secondary battery provided by the invention solves the problems of the traditional Ni (OH)2Poor conductivity of the anode, slow kinetics in the charging and discharging process, and junctionThe rate capability is obviously improved due to the problems of unstable structure and the like; compared with Ni-Co hydrogen batteries which are not doped with P, the Ni-Co hydrogen batteries have higher discharge platforms and higher specific capacities, and have more advantages for future commercialization.
According to the invention, electrochemical tests are carried out on the assembled battery, and according to the theoretical potential of the phosphorus-doped nickel cobalt anode of 0.5V and the theoretical potential of the negative electrode HER/HOR of-0.83V under an alkaline condition, after corresponding overpotentials are considered, the water system phosphorus-doped nickel cobalt-hydrogen secondary battery is selected to work in a voltage window of 0.8V-1.5V, and good multiplying power performance and cycle stability are shown.
The result shows that the anode for the nickel-hydrogen secondary battery has higher discharge platform and specific capacity, excellent rate performance and excellent cycle life, and almost no obvious capacity attenuation can reach 5000 circles.
The invention adopts an electrochemical deposition method with simpler steps and safer operation, and has the advantages and potential of large-scale expanded production.
In order to further understand the present invention, the following examples are provided to illustrate the positive electrode for nickel-metal hydride secondary battery, the method for preparing the same, and the nickel-metal hydride secondary battery provided by the present invention, and the scope of the present invention is not limited by the following examples.
The raw materials used in the invention are all commonly used raw materials in the field.
Example 1
Using foamed nickel as a working electrode, Ag/AgCl as a reference electrode, and a platinum sheet as a counter electrode, and performing electrodeposition for 10 circles in a mixed solution of 0.1mol/L cobalt nitrate, 0.1mol/L nickel nitrate and 0.05mol/L sodium hypophosphite, wherein a current-voltage curve in the deposition process is shown in figure 2, wherein the deposition voltage is-1.2V to 0.2V, and the deposition current range is-4 mA to 2.5 mA.
Example 2
Carbon cloth is used as a working electrode, Ag/AgCl is used as a reference electrode, a platinum sheet is used as a counter electrode, electrodeposition is carried out for 10 circles in a mixed solution of 0.1mol/L cobalt nitrate, 0.2mol/L nickel nitrate and 0.05mol/L sodium hypophosphite, and a current-voltage curve in the deposition process is similar to that in figure 2, which shows that the method has no substrate dependence and universality.
Example 3
The method is characterized in that foamy copper is used as a working electrode, Ag/AgCl is used as a reference electrode, a platinum sheet is used as a counter electrode, electrodeposition is carried out for 10 circles in a mixed solution of 0.1mol/L cobalt nitrate, 0.1mol/L nickel nitrate and 0.1mol/L sodium hypophosphite, the current-voltage curve in the deposition process is similar to that in figure 2, and the method is further explained to have no substrate dependence and universality.
Example 4
Using foamed nickel as a working electrode, Ag/AgCl as a reference electrode and a platinum sheet as a counter electrode, performing electrodeposition for 25 circles in a mixed solution of 0.1mol/L cobalt nitrate, 0.1mol/L nickel nitrate and 0.05mol/L sodium hypophosphite. Wherein the deposition voltage is-1.2V to 0.2V, and the deposition current is in the range of-4 mA to 2.5 mA. The phosphorus-doped nickel-cobalt electrode obtained by electrochemical deposition for 25 circles is characterized in morphology by using a Scanning Electron Microscope (SEM), as shown in FIG. 3, the phosphorus-doped nickel-cobalt positive electrode can be seen to be in a 3D nanosheet or nanoflower-shaped morphology under 500nm, the number of active sites of the reaction is increased, and excellent and rapid electrochemical performance is facilitated.
Example 5
Using foamed nickel as a working electrode, Ag/AgCl as a reference electrode and a platinum sheet as a counter electrode, and carrying out electrodeposition for 20 circles in a mixed solution of 0.1mol/L cobalt nitrate, 0.1mol/L nickel nitrate and 0.05mol/L sodium hypophosphite. Wherein the deposition voltage is-1.2V to 0.2V, and the deposition current is in the range of-4 mA to 2.5 mA. A phosphorus-doped nickel-cobalt electrode obtained by 20 circles of electrodeposition is used as a working electrode, Ag/AgCl is used as a reference electrode, a platinum sheet is used as a counter electrode, an electrolyte is a KOH solution with the concentration of 0.1mol/L, a battery is assembled in a three-electrode system for testing (a nickel-cobalt electrode not doped with P is used as the working electrode, and other conditions are unchanged and used as a comparison sample), and an electrochemical impedance spectrum is adopted for analysis. As shown in fig. 4, the phosphorus-doped nickel-cobalt positive electrode has lower ohmic resistance and charge transfer resistance than the comparative sample, indicating that the phosphorus-doped nickel-cobalt positive electrode has better conductivity and faster electron transfer kinetics.
Example 6
The nickel foam is used as a working electrode, Ag/AgCl is used as a reference electrode, a platinum sheet is used as a counter electrode, and electrodeposition is carried out for 20 circles in a mixed solution of 0.1mol/L cobalt nitrate, 0.1mol/L nickel nitrate and 0.05mol/L sodium hypophosphite. Wherein the deposition voltage is-1.2V to 0.2V, and the deposition current is-4 mA to 2.5 mA. The phosphorus-doped nickel-cobalt electrode obtained by 20 circles of electrodeposition was used as a positive electrode, a Pt/C catalyst was used as a negative electrode, a KOH solution with the concentration of 6mol/L was used as an electrolyte, and an aqueous battery separator was directly assembled into a full cell for testing (a nickel-cobalt electrode not doped with P was used as a positive electrode, and other conditions were not changed and used as a control). The hydrogen pressure inside the negative electrode was about 4 atm. The sweep rate was 0.5mV/s, as shown in FIG. 5, and both of them had two pairs of redox peaks corresponding to the redox conversion reactions of nickel and cobalt ions, respectively. Compared with a comparison sample, the phosphorus-doped nickel-cobalt-hydrogen secondary battery obtained by doping P has higher corresponding current and higher oxidation-reduction potential at the same sweep speed.
Example 7
Using foamed nickel as a working electrode, Ag/AgCl as a reference electrode and a platinum sheet as a counter electrode, and carrying out electrodeposition for 20 circles in a mixed solution of 0.1mol/L cobalt nitrate, 0.1mol/L nickel nitrate and 0.05mol/L sodium hypophosphite. Wherein the deposition voltage is-1.2V to 0.2V, and the deposition current is-4 mA to 2.5 mA. The phosphorus-doped nickel-cobalt electrode obtained by 20 circles of electrodeposition was used as a positive electrode, a Pt/C catalyst was used as a negative electrode, KOH solution with the concentration of 7mol/L was used as an electrolyte, and an aqueous battery separator was directly assembled into a full cell for testing (a nickel-cobalt electrode not doped with P was used as a positive electrode, and other conditions were not changed and used as a comparative sample). The hydrogen pressure inside the negative electrode was about 7 atm. And (5) carrying out a constant-current charge-discharge test, wherein the current is 1mA, and both the two discharge platforms are provided with two discharge platforms as shown in figure 6 and are consistent with the result of the cyclic voltammetry curve. At the same rate (5C), the discharge medium voltage of the comparative sample is 1.19V, while the P-doped ni-co-hydrogen secondary battery has a significantly higher discharge medium voltage of 1.26V. Meanwhile, the phosphorus-doped nickel-cobalt-hydrogen secondary battery has higher specific capacity, the specific capacity of the phosphorus-doped nickel-cobalt-hydrogen secondary battery is about 276mAh/g, the specific capacity of the P-undoped nickel-cobalt-hydrogen secondary battery is only 225mAh/g, and the specific capacity is obviously improved.
Example 8
Using foamed nickel as a working electrode, Ag/AgCl as a reference electrode and a platinum sheet as a counter electrode, performing electrodeposition for 25 circles in a mixed solution of 0.1mol/L cobalt nitrate, 0.1mol/L nickel nitrate and 0.05mol/L sodium hypophosphite. Wherein the deposition voltage is-1.2V to 0.2V, and the deposition current is-4 mA to 2.5 mA. A phosphorus-doped nickel-cobalt electrode obtained by 25 circles of electrodeposition is used as a positive electrode, a Pt/C catalyst is used as a negative electrode, a KOH solution with the concentration of 5mol/L is used as an electrolyte, and an aqueous battery diaphragm is directly assembled into a full battery for testing, and a cycle stability test is carried out (the discharge depth is 50%). The hydrogen pressure inside the negative electrode was about 10 atm. As shown in fig. 7, the coulombic efficiency can reach more than 99% in the circulation process. The phosphorus-doped nickel-cobalt-hydrogen secondary battery can keep stable coulombic efficiency and capacity in 5000 cycles, is excellent in stability, and has obvious advantages for practical large-scale application.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (12)
1. The positive electrode for the nickel-hydrogen secondary battery is characterized by comprising a positive electrode substrate and a phosphorus-doped nickel-cobalt mixed positive electrode material layer compounded on the surface of the positive electrode substrate;
the preparation method of the positive electrode for the nickel-hydrogen secondary battery comprises the following steps:
and depositing a phosphorus-doped nickel-cobalt mixed positive electrode material layer on the surface of the positive electrode substrate by a dynamic electrochemical deposition method to obtain the positive electrode for the nickel-hydrogen secondary battery.
2. The positive electrode according to claim 1, wherein the positive electrode substrate is selected from a carbon material substrate or a metal substrate;
the carbon material substrate is at least one of carbon cloth, modified carbon cloth, carbon paper, modified carbon paper, carbon felt, modified carbon felt, graphite felt, modified graphite felt, carbon micro-fiber, carbon nano-fiber, modified carbon micro-fiber and modified carbon nano-fiber;
the metal substrate is foamed nickel, foamed copper, nickel foil, copper foil, titanium foil or titanium mesh.
3. A method for producing a positive electrode according to any one of claims 1 to 2, comprising the steps of:
and depositing a phosphorus-doped nickel-cobalt mixed positive electrode material layer on the surface of the positive electrode substrate by a dynamic electrochemical deposition method to obtain the positive electrode for the nickel-hydrogen secondary battery.
4. The method according to claim 3, wherein the electrolyte contains cobalt nitrate in an amount of 0.001 to 10mol/L, nickel nitrate in an amount of 0.001 to 10mol/L, and sodium hypophosphite in an amount of 0.001 to 2 mol/L.
5. The method according to claim 3, wherein the voltage for deposition in the dynamic electrochemical deposition method is from-1.2V to 0.2V.
6. The method according to claim 3, wherein the number of deposition cycles in the dynamic electrochemical deposition method is 5 to 50 cycles.
7. The method of claim 3, wherein the dynamic electrochemical deposition is performed in a three-electrode system, wherein the working electrode is a positive substrate, the reference electrode is Ag/AgCl, and the counter electrode is a platinum sheet.
8. A nickel-metal hydride secondary battery comprising a positive electrode, a negative electrode, a separator and an electrolyte, wherein the positive electrode is selected from the positive electrodes according to any one of claims 1 to 2.
9. The nickel-hydrogen secondary battery according to claim 8, wherein the negative electrode is a current collector loaded with a catalyst selected from one or more of non-noble metals, and carbon materials;
the electrolyte is a strong alkali aqueous solution; the concentration of strong base in the electrolyte is 0.01-10 mol/L;
the separator is selected from water-based battery separators.
10. The nickel-hydrogen secondary battery according to claim 9, wherein the non-noble metal catalyst comprises Ni, NiN, NiS, NiP, NiPS, NiMo, NiCoMo, MoO2、MoS2、MoC、MoC2、MoP、WO2、WS2、WC、WC2And WP; the noble metal catalyst comprises one or more of Pt, Pd, Ir, and Ru; the carbon material comprises one of a micro-or nanoparticle, a micro-or nanowire, a micro-or nanosheet, or a micro-or nanotube structure.
11. The nickel-hydrogen secondary battery according to claim 9, characterized in that the micro-or nanoparticles are selected from micro-or nanospheres.
12. The nickel-hydrogen secondary battery according to claim 8, wherein the hydrogen gas pressure inside the secondary battery negative electrode is 1 to 100 atm;
the structure of the secondary battery includes a button type battery or a cylindrical type battery.
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