Microrod-shaped iron-based double metal oxide and preparation method and application thereof

Abstract

The present application relates to the technical field of electrode material, in particular to a kind of microrod-shaped iron-based bimetallic oxide and its preparation method and application.Method: 1,5-pentanediol, water and ethylenediamine are mixed to obtain a mixed solvent;Soluble iron salt and soluble metal salt are dissolved in the mixed solvent, and hydrothermal reaction is carried out to obtain microrod-shaped iron-based bimetallic oxide;Wherein, soluble metal salt is selected from soluble zinc salt, soluble nickel salt, soluble copper salt or soluble cobalt salt.The microrod-shaped iron-based bimetallic oxide prepared by solvothermal method through one-step reaction presents fusiform solid structure, and its structural stability is strong.The microrod-shaped iron-based bimetallic oxide negative electrode prepared by using it as raw material can effectively maintain the solid microrod structure and is not prone to powdering phenomenon during charge-discharge cycle, thereby improving the specific capacity and cycle stability of lithium ion battery under high current density, and overcoming the defects existing in prior art.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrode materials, in particular to a microrod-shaped iron-based double metal oxide and a preparation method and application thereof. BACKGROUND

[0002] Since lithium ion batteries entered the market in 1991, they have developed from power sources for small appliances to driving power sources for electric vehicles. Currently, the theoretical specific capacity of commercialized graphite-based carbon negative electrode materials is only 372 mAh / g, and lithium dendrites are easily formed during rapid charging, causing short circuits in the battery and safety problems. Therefore, developing negative electrode materials with higher specific capacity, good safety and long cycle life has become a hot topic in the research of lithium ion batteries. In recent years, iron-based double metal oxide (MFe2O4, M=Co, Zn, Ni, Cu) negative electrode materials have attracted widespread attention due to their high theoretical specific capacity (>900 mAh / g). However, due to the "conversion type" lithium storage mechanism of iron-based double metal oxides, the phase transition and large volume change of the material during the cycle process easily cause material pulverization, and there are still defects such as low charge-discharge capacity and poor cycle stability at high current density.

[0003] Researchers often use methods such as constructing porous micro-nano hierarchical structures or nanosizing materials to buffer the large volume change to solve the above problems. However, the tap density of porous materials and nanosized materials is not high, which is not conducive to improving the energy density of the battery. In addition, nanosized materials are difficult to mix and require more conductive agents and binders when making electrode sheets. In contrast, solid micrometer-sized negative electrode materials are more ideal. How to simply prepare micrometer-sized negative electrode materials with high activity and long cycle life is an important topic for the development of lithium ion batteries.

[0004] Currently, the existing methods for preparing iron-based double metal oxides reported mainly include hydrothermal method, solvothermal method, electrospinning method and template method. Among them, the hydrothermal method and the solvothermal method often use surfactants to control the morphology and size of the material, increasing the cost and making it difficult to recycle and treat the waste liquid. The material prepared by the electrospinning method is nanofibrous, and the preparation cost is high. The microstructure of the material determines its low tap density, which is difficult to improve the energy density of the battery. The template method has a complicated preparation process, and the use of templates increases the steps and the synthesis cost. SUMMARY

[0005] In view of the deficiencies of the prior art, the micron rod-shaped iron-based double metal oxide and its preparation method and application are provided, the micron rod-shaped iron-based double metal oxide (MFe2O4, M=Co or Zn or Ni or Cu) is prepared by a one-step reaction through a solvothermal method, using 1,5-pentanediol, water and ethylenediamine as solvent media, and using soluble iron salt and soluble metal salt (soluble zinc salt, soluble nickel salt, soluble copper salt or soluble cobalt salt) as raw materials, without additional addition of surfactants and templates, and the micron rod-shaped iron-based double metal oxide presents a spindle-shaped solid structure, and has strong structural stability, and the morphology of the micron rod can be effectively maintained and is not prone to powdering phenomenon in the charging and discharging cycle process, overcoming the defects of the prior art.

[0006] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is:

[0007] The first object of the present application is to provide a preparation method of micron rod-shaped iron-based double metal oxide, comprising the following steps:

[0008] S1, using 1,5-pentanediol and water as solvents, and ethylenediamine as an alkali source, mixing the solvents and the alkali source to obtain a mixed solvent. Among them, ethylenediamine is used as an alkali source to provide alkaline reaction conditions, and non-alkaline conditions cannot react to generate micron rod-shaped iron-based double metal oxide; in addition, 1,5-pentanediol, water and ethylenediamine are reaction solvent media, and together with ethylenediamine, they control the morphology and size of the micron rod-shaped iron-based double metal oxide, and if other alkali sources are used, although the reaction can be carried out, the solid micron rod product cannot be obtained.

[0009] S2, the soluble iron salt and the soluble metal salt are dissolved in the mixed solvent together, and a hydrothermal reaction is carried out, in the hydrothermal reaction process, the ethylenediamine in the mixed solvent is ionized to generate hydroxyl ions, and at the same time, the metal salt ions and the hydroxyl ions react to form a double metal oxide, and the micron rod-shaped iron-based double metal oxide is obtained. 3+

[0010] Among them, the soluble metal salt is selected from soluble zinc salt, soluble nickel salt, soluble copper salt or soluble cobalt salt. Taking the soluble metal salt as the soluble cobalt salt as an example, the mechanism is: H2NCH2CH2NH2+2H2O⇌H3NCH2CH2NH3 2+ +2OH - 、Co 2+ +2Fe 3+ +8OH − →CoFe2O4+4H2O.

[0011] Preferably, the Fe 3+ ​The microrod-shaped iron-based bimetallic oxide of the present application is a single-phase substance, such as CoFe2O4, with a fixed element composition ratio, and the molar ratio of the metal ions in the soluble metal salt is 2:1.

[0012] Preferably, in the mixed solvent, the volume ratio of 1,5-pentanediol, ethylenediamine and water is 4-6:5-10:1.

[0013] Preferably, the hydrothermal reaction is carried out at 150-180°C for 4-7h.

[0014] Preferably, the microrod-shaped iron-based bimetallic oxide prepared is further subjected to washing and drying treatment, and the drying treatment is carried out at 70-90°C.

[0015] The second object of the present application is to provide the microrod-shaped iron-based bimetallic oxide prepared by the above preparation method.

[0016] Preferably, the microrod-shaped iron-based bimetallic oxide has a spindle-shaped solid structure.

[0017] Preferably, the microrod-shaped iron-based bimetallic oxide has monodispersity, the length of the microrod-shaped iron-based bimetallic oxide is 0.6-2.0μm, the maximum diameter of the middle part is 0.2-0.4μm, and the specific surface area is 5-10m 2 2 / g.

[0018] The third object of the present application is to provide a microrod-shaped iron-based bimetallic oxide negative electrode, which is prepared by using the above microrod-shaped iron-based bimetallic oxide, a conductive agent, a binder, a solvent and a current collector, dissolving the microrod-shaped iron-based bimetallic oxide, the conductive agent and the binder in the solvent to prepare a slurry, and loading the slurry on the current collector to obtain the microrod-shaped iron-based bimetallic oxide negative electrode.

[0019] Preferably, the mass ratio of the microrod-shaped iron-based bimetallic oxide, the conductive agent and the binder is 75-80:10-15:10.

[0020] Preferably, the conductive agent is selected from Super P or conductive carbon black, acetylene black.

[0021] Preferably, the binder is polyvinylidene fluoride.

[0022] Preferably, the solvent is N-methylpyrrolidone.

[0023] Preferably, the current collector is copper foil.

[0024] The fourth object of the present application is to provide a lithium ion battery, which is prepared by using the microrod-shaped iron-based bimetallic oxide negative electrode, a positive electrode, a separator and an electrolyte.​

[0025] Compared with the prior art, the present application has the beneficial effects that:

[0026] 1. The present application provides a preparation method of micro-rod-shaped iron-based double metal oxides, wherein 1,5-pentanediol and water are used as solvents, ethylenediamine is used as an alkali source, the solvent and the alkali source are mixed to obtain a mixed solvent, a soluble iron salt and a soluble metal salt are dissolved in the mixed solvent, and a hydrothermal reaction is performed, during which the ethylenediamine in the mixed solvent is ionized to generate hydroxyl ions, and the hydroxyl ions react with the metal salt ions and the iron ions to form double metal oxides, thereby obtaining the micro-rod-shaped iron-based double metal oxides; wherein the soluble metal salt is selected from a soluble zinc salt, a soluble nickel salt, a soluble copper salt, or a soluble cobalt salt. 3+ The present application uses 1,5-pentanediol, water, and ethylenediamine as a solvent medium to control the morphology and size of the micro-rod-shaped iron-based double metal oxides, which saves raw materials and reduces costs without the need for additional surfactants to control the morphology. The micro-rod-shaped iron-based double metal oxides prepared by the one-step reaction of the solvent thermal method have a solid micro-rod structure and excellent stability, which can maintain structural stability during the charging and discharging process of the battery, thereby achieving a long cycle life.

[0027] 2. Compared with the prior art, the preparation method of the present application has the advantages of simple process flow, strong operability, mild reaction conditions, and no need for additional calcination treatment process, thereby effectively saving energy and significantly reducing the stringent requirements for equipment safety performance. At the same time, the preparation method of the present application can realize controllable size of the micro-rod-shaped iron-based double metal oxides with good reproducibility. In addition, the solvent medium used in the present application is low in cost and easy to recycle and reuse, and no pollutants are generated during the preparation process, which is green and environmentally friendly.

[0028] 3. The micro-rod-shaped iron-based double metal oxide negative electrode prepared by using the micro-rod-shaped iron-based double metal oxide prepared by the present application has excellent large-current charging and discharging performance and excellent cycle stability. Specifically, the discharge capacity is as high as 412 mAh / g at a current of 4 A / g. After 1400 cycles of charging and discharging at a current density of 0.5 A / g, the discharge capacity can still reach 688 mAh / g. Therefore, the micro-rod-shaped iron-based double metal oxide negative electrode of the present application can be used as an ideal choice for lithium-ion power batteries and lithium-ion energy storage battery negative electrode materials. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 XRD pattern of CoFe2O4 prepared in Example 1.

[0030] Figure 2 SEM pattern of CoFe2O4 prepared in Example 1.

[0031] Figure 3 TEM image of CoFe2O4 prepared for Example 1.

[0032] Figure 4 Rate capability plot of the coin cell prepared for CoFe2O4 of Application Example 1.

[0033] Figure 5 Long cycle performance plot of the coin cell prepared for CoFe2O4 of Application Example 1.

[0034] Figure 6 SEM image of the electrode sheet after 400 cycles for CoFe2O4 of Application Example 1.

[0035] Figure 7 SEM image of ZnFe2O4 prepared for Example 2.

[0036] Figure 8 SEM image of NiFe2O4 prepared for Example 3.

[0037] Figure 9 SEM image of CuFe2O4 prepared for Example 4. DETAILED DESCRIPTION

[0038] The technical solutions of the present application will be described clearly and completely below in combination with the data in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0039] It should be noted that the professional terms used in the present application are only for the purpose of describing the specific embodiments, and are not intended to limit the scope of protection of the present application. Unless otherwise specified, the various raw materials, reagents, instruments and equipment used in the following embodiments of the present application can be purchased from the market or prepared by the existing method.

[0040] In the prior art, the reported existing methods for preparing iron-based bimetallic oxides mainly include hydrothermal method, solvothermal method, electrospinning method and template method. Among them, the hydrothermal method and the solvothermal method use surfactants to control the material morphology size, which increases the cost and the waste liquid is not easy to recover and process. The material prepared by electrospinning is nanofiber, which has high preparation cost, and the microstructure of the material determines that the compaction density is low, which is difficult to improve the energy density of the battery. The template method has a complicated preparation process, and the use of templates increases the steps and the synthesis cost.

[0041] In view of the problems in the prior art, the application provides a preparation method of a microrod-shaped iron-based double metal oxide, which comprises the following steps: mixing 1,5-pentanediol, water and ethylenediamine to obtain a mixed solvent; dissolving a soluble iron salt and a soluble metal salt in the mixed solvent to perform a hydrothermal reaction; in the hydrothermal reaction process, the ethylenediamine in the mixed solvent is ionized to generate hydroxyl ions, meanwhile, the hydroxyl ions react with the metal salt ions to form a double metal oxide, so that the microrod-shaped iron-based double metal oxide is obtained; and the soluble metal salt is selected from a soluble zinc salt, a soluble nickel salt, a soluble copper salt or a soluble cobalt salt. 3+

[0042] In view of the problems of material pulverization caused by a huge volume change, low charge-discharge capacity under a high current density and poor cycle stability of the iron-based double metal oxide in the cycle process, the microrod-shaped iron-based double metal oxide (MFe2O4) with a shuttle-shaped solid structure is prepared by using a specific solvent system (1,5-pentanediol / water / ethylenediamine) one-step solvothermal method, so that the problems are overcome.

[0043] In view of the problems of low tap density or electrode processing difficulty (more conductive agent and binder are needed for nanomaterials, and slurry mixing is difficult) of the materials prepared by the existing methods (hydrothermal method, solvothermal method need to add a surfactant, electrospinning method obtains nanofibers, and the template method is complicated), the target product is obtained by using only 1,5-pentanediol, water and ethylenediamine as a mixed solvent medium without additional addition of a surfactant and a template agent, one-step solvothermal reaction, and the solvent has low cost, is easy to recycle and has a green and environmentally-friendly process, so that the problems are overcome.

[0044] In order for those skilled in the art to more clearly understand the technical solutions of the application, the technical solutions of the application will be described in detail below with reference to specific embodiments:

[0045] Embodiment 1

[0046] A preparation method of a microrod-shaped iron-based double metal oxide comprises the following steps:

[0047] S1, 2mmol of cobalt nitrate hexahydrate and 4mmol of iron nitrate nonahydrate are dissolved in a mixed solvent composed of 25mL of 1,5-pentanediol, 5mL of deionized water and 5mL of ethylenediamine to obtain a clear solution after stirring.

[0048] S2, the clear solution is transferred to a hydrothermal reaction kettle, heated to 170℃ and kept at a constant temperature for 6h, after the reaction kettle is cooled to room temperature, the precipitate is collected by filtration and repeatedly washed with deionized water, and dried at 80℃ to obtain a microrod-shaped iron-based double metal oxide, which is recorded as CoFe2O4.

[0049] Embodiment 2​

[0050] A preparation method of a microrod-shaped iron-based double metal oxide, comprising the following steps:

[0051] S1, 2mmol of zinc nitrate hexahydrate and 4mmol of iron nitrate nonahydrate are dissolved in a mixed solvent composed of 20mL of 1,5-pentanediol, 5mL of deionized water and 4mL of ethylenediamine, and stirred uniformly to obtain a clear solution.

[0052] S2, the clear solution is transferred to a hydrothermal reaction kettle, heated to 170 DEG C and kept constant for 6h; after the reaction kettle is cooled to room temperature, the precipitate is collected by filtration, repeatedly washed with deionized water, and dried at 80 DEG C, to obtain a microrod-shaped iron-based double metal oxide, denoted as ZnFe2O4.

[0053] Example 3

[0054] A preparation method of a microrod-shaped iron-based double metal oxide, comprising the following steps:

[0055] S1, 2mmol of zinc nitrate hexahydrate and 4mmol of iron nitrate nonahydrate are dissolved in a mixed solvent composed of 20mL of 1,5-pentanediol, 5mL of deionized water and 4mL of ethylenediamine, and stirred uniformly to obtain a clear solution.

[0056] S2, the clear solution is transferred to a hydrothermal reaction kettle, heated to 170 DEG C and kept constant for 6h; after the reaction kettle is cooled to room temperature, the precipitate is collected by filtration, repeatedly washed with deionized water, and dried at 80 DEG C, to obtain a microrod-shaped iron-based double metal oxide, denoted as ZnFe2O4.

[0057] Example 4

[0058] A preparation method of a microrod-shaped iron-based double metal oxide, comprising the following steps:

[0059] S1, 2mmol of zinc nitrate hexahydrate and 4mmol of iron nitrate nonahydrate are dissolved in a mixed solvent composed of 20mL of 1,5-pentanediol, 5mL of deionized water and 4mL of ethylenediamine, and stirred uniformly to obtain a clear solution.

[0060] S2, the clear solution is transferred to a hydrothermal reaction kettle, heated to 170 DEG C and kept constant for 6h; after the reaction kettle is cooled to room temperature, the precipitate is collected by filtration, repeatedly washed with deionized water, and dried at 80 DEG C, to obtain a microrod-shaped iron-based double metal oxide, denoted as ZnFe2O4.

[0061] By Figure 1 It is concluded that the microrod-shaped iron-based double metal oxide prepared in the example 1 of the present application has a CoFe2O4 spinel phase structure, and high crystallinity.

[0062] ByFigure 2 It is concluded that the CoFe2O4 prepared in the embodiment 1 of the present application presents a shuttle-shaped solid structure microrod morphology and has monodispersity. The length of the shuttle-shaped microrod is 1.2 μm-2.0 μm, and the maximum diameter of the middle part of the shuttle-shaped microrod is about 0.38 μm. It is observed that the CoFe2O4 microrod has a uniform size and a uniform shape. Figure 3 It is further verified that the CoFe2O4 solid microrod structure has a characteristic.

[0063] It is concluded that the ZnFe2O4 prepared in the embodiment 2 of the present application presents a shuttle-shaped microrod morphology. The length of the shuttle-shaped microrod is 0.6 μm-1.2 μm, and the maximum diameter of the middle part of the shuttle-shaped microrod is about 0.2 μm. Figure 7 It is concluded that the NiFe2O4 prepared in the embodiment 3 of the present application presents a shuttle-shaped microrod morphology. The length of the shuttle-shaped microrod is 0.8 μm-1.1 μm, and the maximum diameter of the middle part of the shuttle-shaped microrod is about 0.2 μm.

[0064] Figure 8 It is concluded that the CuFe2O4 material prepared in the embodiment 4 of the present application presents a shuttle-shaped microrod morphology and has monodispersity. The length of the shuttle-shaped microrod is 0.8 μm-1.6 μm, and the maximum diameter of the middle part of the shuttle-shaped microrod is about 0.3 μm.

[0065] The microrod-shaped iron-based bimetallic oxide is prepared in the embodiments 1-4 of the present application, and the effects are parallel. Taking the microrod-shaped iron-based bimetallic oxide prepared in the embodiment 1 as an example, the microrod-shaped iron-based bimetallic oxide negative electrode is prepared. The CoFe2O4, Super P conductive carbon and polyvinylidene fluoride binder are mixed in a mass ratio of 75:15:10, N-methyl pyrrolidone solvent is added and stirred uniformly to prepare a slurry. The slurry is coated on a copper foil and vacuum dried at 70°C to obtain the microrod-shaped iron-based bimetallic oxide negative electrode. Figure 9 The microrod-shaped iron-based bimetallic oxide negative electrode is assembled into a button cell, a metal lithium sheet is used as a counter electrode, a polypropylene porous film is used as a separator, 1 mol of lithium hexafluorophosphate is dissolved in 1 L of a mixed solvent composed of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate to prepare an electrolyte, and a CR2016 button cell is assembled.

[0066] The electrochemical performance of the microrod-shaped iron-based bimetallic oxide negative electrode is studied. The constant current charge and discharge test is carried out on a CT2001A battery test system, and the voltage range is 0.01 V-3 V. The specific conditions are as follows.

[0067] The microrod-shaped iron-based bimetallic oxide negative electrode is assembled into a button cell, a metal lithium sheet is used as a counter electrode, a polypropylene porous film is used as a separator, 1 mol of lithium hexafluorophosphate is dissolved in 1 L of a mixed solvent composed of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate to prepare an electrolyte, and a CR2016 button cell is assembled.

[0068] The microrod-shaped iron-based bimetallic oxide negative electrode is assembled into a button cell, a metal lithium sheet is used as a counter electrode, a polypropylene porous film is used as a separator, 1 mol of lithium hexafluorophosphate is dissolved in 1 L of a mixed solvent composed of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate to prepare an electrolyte, and a CR2016 button cell is assembled.

[0069] Figure 4 ​​It is concluded that the average discharge capacity at a current density of 0.2 A / g is as high as 800 mAh / g, and the average discharge capacity at a large current density of 4 A / g is still 412 mAh / g, showing excellent high-rate performance.

[0070] It is concluded that the average discharge capacity at a current density of 0.2 A / g is as high as 800 mAh / g, and the average discharge capacity at a large current density of 4 A / g is still 412 mAh / g, showing excellent high-rate performance. Figure 5 It is concluded that the average discharge capacity at a current density of 0.2 A / g is as high as 800 mAh / g, and the average discharge capacity at a large current density of 4 A / g is still 412 mAh / g, showing excellent high-rate performance.

[0071] It is concluded that the average discharge capacity at a current density of 0.2 A / g is as high as 800 mAh / g, and the average discharge capacity at a large current density of 4 A / g is still 412 mAh / g, showing excellent high-rate performance. Figure 6 It is concluded that the average discharge capacity at a current density of 0.2 A / g is as high as 800 mAh / g, and the average discharge capacity at a large current density of 4 A / g is still 412 mAh / g, showing excellent high-rate performance.

[0072] It is concluded that the average discharge capacity at a current density of 0.2 A / g is as high as 800 mAh / g, and the average discharge capacity at a large current density of 4 A / g is still 412 mAh / g, showing excellent high-rate performance. It is to be understood that, when numerical ranges are involved in the present application, both the endpoints and any number between the endpoints are included. Since the steps and embodiments are the same, the preferred embodiments are described in the present application. Although the preferred embodiments of the present application have been described, those skilled in the art can make further changes and modifications to the embodiments once they know the basic inventive concept. Therefore, the appended claims are intended to include the preferred embodiments and all changes and modifications falling within the scope of the present application.

Claims

1. A method for preparing a micron-sized rod-shaped iron-based bimetallic oxide, characterized in that, Includes the following steps: Using 1,5-pentanediol and water as solvents and ethylenediamine as a base source, the solvent and base source are mixed to obtain a mixed solvent; A soluble iron salt and a soluble metal salt are dissolved together in a mixed solvent and subjected to a hydrothermal reaction. During the hydrothermal reaction, ethylenediamine in the mixed solvent ionizes to generate hydroxide ions, while Fe... 3+ Metal salt ions react together with hydroxide ions to form bimetallic oxides, resulting in micron-sized rod-shaped iron-based bimetallic oxides. The micron-shaped rod-shaped iron-based bimetallic oxide exhibits a spindle-shaped solid structure; The soluble metal salt is selected from soluble zinc salt, soluble nickel salt, soluble copper salt, or soluble cobalt salt. Fe in soluble iron salts 3+ The molar ratio of the metal ions in the soluble metal salt is 2:1; The hydrothermal reaction conditions are: reacting at 150℃~180℃ for 4h~7h.

2. A micron-sized rod-shaped iron-based bimetallic oxide, characterized in that, The micron-shaped rod-shaped iron-based bimetallic oxide is prepared by the preparation method described in claim 1, and the micron-shaped rod-shaped iron-based bimetallic oxide exhibits a spindle-shaped solid structure. The micron-sized rod-shaped iron-based bimetallic oxides exhibit monodispersity, with lengths ranging from 0.6 μm to 2.0 μm, a maximum diameter at the center of 0.2 μm to 0.4 μm, and a specific surface area of ​​5 m². 2 / g~10m 2 / g.

3. A micron-sized rod-shaped iron-based bimetallic oxide negative electrode, characterized in that, The micron-shaped iron-based bimetallic oxide anode is prepared by the micron-shaped iron-based bimetallic oxide, conductive agent, binder, solvent and current collector as described in claim 2. The micron-shaped iron-based bimetallic oxide, conductive agent and binder are dissolved together in the solvent to prepare a slurry; the slurry is loaded onto the current collector and dried to obtain the micron-shaped iron-based bimetallic oxide anode.

4. The micron-shaped rod-shaped iron-based bimetallic oxide negative electrode according to claim 3, characterized in that, The mass ratio of micron-sized rod-shaped iron-based bimetallic oxide, conductive agent, and binder is 75~80:10~15:

10.

5. A lithium-ion battery, characterized in that, The lithium-ion battery is made from the micron rod-shaped iron-based bimetallic oxide negative electrode, positive electrode, separator and electrolyte as described in claim 3.

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