CN110808359A - MnO (MnO)2Preparation method of/rGO/PANI aerogel and application of aerogel in water-based zinc ion battery - Google Patents

MnO (MnO)2Preparation method of/rGO/PANI aerogel and application of aerogel in water-based zinc ion battery Download PDF

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CN110808359A
CN110808359A CN201910755490.9A CN201910755490A CN110808359A CN 110808359 A CN110808359 A CN 110808359A CN 201910755490 A CN201910755490 A CN 201910755490A CN 110808359 A CN110808359 A CN 110808359A
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mno
rgo
pani
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曹澥宏
毛静
毋芳芳
施文慧
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Zhejiang University of Technology ZJUT
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Abstract

The invention relates to the technical field of composite materials, and aims to solve the problem of traditional MnO2The problem that the capacity is rapidly reduced due to the gradual dissolution of manganese in the electrolyte in the aqueous zinc ion battery is solved, and MnO is provided2Preparation method of/rGO/PANI aerogel and application thereof in water-based zinc ion battery, wherein MnO is2The preparation method of the/rGO/PANI aerogel is characterized by comprising the following steps: (1) uniformly mixing the graphene oxide dispersion liquid and manganese dioxide particles under a closed condition, and heating for reaction to obtain MnO2A GO hydrogel; (2) MnO of2Heating reduction reaction of/GO hydrogel to obtain MnO2/rGO hydrogels(ii) a (3) MnO is added into mixed aqueous solution containing aniline monomer and hydrochloric acid2Adding mixed aqueous solution of ammonium persulfate and hydrochloric acid into the rGO hydrogel, carrying out polymerization reaction, washing and vacuum drying to obtain MnO2a/rGO/PANI aerogel. The method has the advantages of simple operation, mild condition, adjustable appearance, controllable structure, uniform component distribution and batch or industrial production.

Description

MnO (MnO)2Preparation method of/rGO/PANI aerogel and application of aerogel in water-based zinc ion battery
Technical Field
The invention relates to the technical field of composite materials, in particular to MnO2A preparation method of/rGO/PANI aerogel and an application of the/rGO/PANI aerogel in a water-based zinc ion battery.
Background
With the rapid development of the world, people are looking for safer and more environmentally friendly batteries to replace lithium ion batteries. Nowadays, water-based zinc ion batteries are receiving attention because of their abundant global resources, low flammability, low material cost, and large-scale development. Zinc metal is an advantageous anode for aqueous batteries because it has a low redox potential (-0.76V relative to a standard hydrogen electrode) and a high theoretical capacity (820mAh g)-1) And has good water compatibility.
MnO compared to Prussian blue analogues and vanadium based materials2The electrode material has the highest theoretical capacity in the water-based zinc ion battery. However, MnO2Electrode materials have poor rate performance and cycle sustainability. This is probably because of the presence of Zn2+In the intercalation process, Mn is gradually dissolved in the electrolyte to change MnO2Balance of Mn in the electrode material. In order to solve the problem of continuous dissolution of Mn element, Liu et al have adopted MnO in water system2Addition of MnSO to Zn Battery4Electrolyte to pre-balance MnO2Mn in electrodes and electrolytes2+(Nature energy 2016,1, 16039); chenjun et al reported a new ZnMn2O4The/carbon composite material adopts Zn (CF) in the process of intercalation and deintercalation of zinc ions3SO3)2The electrolyte was used to inhibit the dissolution of Mn (J.Am.chem.Soc.2016,138, 12894-12901).
Although these methods described above all show good rate and cycle performance, the following disadvantages still remain: (1) MnSO4Mn in (1)2+Will deposit again to form new active species (side reactions); (2) additives can increase the cost of large scale applications, while Zn (CF)3SO3)2The price is high; (3) for micro-energy storage devices, additives can increase the weight of the overall device and reduce the energy density.
Disclosure of Invention
The invention aims to overcome the traditional MnO2The problem that the capacity is rapidly reduced due to the gradual dissolution of manganese in the electrolyte in the aqueous zinc ion battery is solved, and MnO is provided2The preparation method of/rGO/PANI aerogel has the advantages of simple operation, controllable conditions, wide sources of used reagent instruments, mass or industrial production and capability of preparing MnO2PerGO/PANI aerogels versus traditional MnO2Electrode material, MnO coated with PANI2the/rGO aerogel has excellent rate capability and long cycle stability.
The invention also provides MnO2The application of the/rGO/PANI aerogel in an aqueous zinc ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
MnO (MnO)2The preparation method of the/rGO/PANI aerogel comprises the following steps:
(1) uniformly mixing the graphene oxide dispersion liquid and manganese dioxide particles under a closed condition, transferring the mixture into an autoclave, and heating for reaction to obtain MnO2A GO hydrogel; the manganese dioxide particles used in the step are obtained by ball milling commercial manganese dioxide particles (with the purity of 99.9%) for 16-48 hours at 400 rpm; mixing under a violent stirring condition for 10-60 min, preferably 30 min;
(2) MnO obtained in the step (1)2Soaking GO hydrogel in deionized water, adding a reducing agent, transferring the mixture into a high-pressure kettle, and heating for reduction reaction to obtain MnO2a/rGO hydrogel;
(3) adding MnO obtained in the step (2) into a mixed aqueous solution containing aniline monomer and hydrochloric acid2Adding mixed aqueous solution of ammonium persulfate and hydrochloric acid into the rGO hydrogel, carrying out polymerization reaction under the ice-water bath condition, washing the obtained sample, and drying in vacuum to obtain MnO2a/rGO/PANI aerogel.
The invention utilizes water heatMethod for reaction, polymerization reaction and vacuum drying, MnO with adjustable appearance, controllable structure and uniform component distribution2The invention relates to a/rGO/PANI aerogel, which is prepared by adding MnO with different contents into graphene oxide liquid crystal based on the colloid liquid crystal theory by means of the property of graphene oxide liquid crystal2Powder, MnO is prepared by hydrothermal reaction2Adding a reducing agent into the/GO hydrogel, and chemically reducing to obtain MnO2Performing chemical oxidation polymerization on the surface of the assembly to obtain a PANI layer, and finally performing vacuum drying to obtain high-density MnO2a/rGO/PANI aerogel. The preparation method of the aerogel is simple to operate, controllable in conditions, wide in source of used reagent instruments and capable of realizing batch or industrial production; the technical scheme of the invention is simple, and can be realized by only two steps of hydrothermal reaction, polymerization reaction in ice-water bath and vacuum drying; the solvent used in the invention is easy to obtain in laboratories or industrial production, has low price and wide source, and has no special requirements on experimental equipment.
Preferably, in the step (1), the charging mass ratio of the manganese dioxide particles to the graphene oxide is (1-10): 1; the average particle diameter of the manganese dioxide particles is 500 nm-3 mu m.
Preferably, the graphene oxide has a sheet structure, and the lateral dimension of the graphene oxide is 0.1-100 μm, and more preferably 20-30 μm.
Preferably, in the step (1), the heating temperature is 120-180 ℃, and the heating time is 3-6 h, more preferably 3 h.
Preferably, in the step (1), the concentration of the graphene oxide dispersion liquid is 0.01-50 mg/mL, and more preferably 2-4 mg/mL.
Preferably, in step (2), the reducing agent is ascorbic acid; the feeding mass ratio of the ascorbic acid to the graphene oxide is (1-10): 1.
preferably, in the step (2), the temperature of the heating reduction reaction is 100-150 ℃ and the time is 3-6 h.
Preferably, in the step (3), the concentration of the aniline monomer in the mixed aqueous solution containing the aniline monomer and hydrochloric acid is 0.12-0.16M, and more preferably 0.12M; the concentration of the hydrochloric acid is 0.5-2M.
Preferably, in the step (3), the concentration of ammonium persulfate in the mixed aqueous solution of ammonium persulfate and hydrochloric acid is 0.12-0.16M; the concentration of the hydrochloric acid is 1M.
Preferably, in the step (3), the temperature of the polymerization reaction is controlled to be 0-4 ℃, and the time of the polymerization reaction is controlled to be 1-2 hours, preferably 1 hour; the vacuum degree of vacuum drying is-30 kPa, the temperature is 40-80 ℃, and the time is 24-48 h.
MnO prepared by any one of the methods2Application of the/rGO/PANI aerogel in an aqueous zinc ion battery. The MnO2MnO of/rGO/PANI aerogel2The crystal, the graphene sheet layer and the polyaniline are formed, the structural integrity of each component is kept in the synthesis process, and the composite material has MnO function2The excellent performances of graphene and polyaniline are synergistic, the excellent performances of the graphene and the polyaniline can be simultaneously exerted in the fields of energy storage, sensing, catalysis, adsorption and the like, and MnO wrapped by polyaniline2the/rGO can inhibit the dissolution of manganese to a certain extent, and has bright application prospect in the field of water-based zinc ion batteries.
Therefore, the invention has the following beneficial effects:
(1) the preparation method has the advantages of simple operation, mild condition, adjustable appearance, controllable structure and uniform component distribution, and can be used for batch or industrial production;
(2) MnO prepared by the method of the invention2the/rGO/PANI aerogel retains graphene and MnO2The structural integrity of the three-dimensional compact assembly body with the crystal and the polyaniline as templates has the advantages of graphene and MnO2Excellent properties of crystals and polyaniline;
(3)MnO2MnO in/rGO/PANI aerogel2The coating is tightly wrapped by rGO and polyaniline, and the dissolution of Mn is effectively inhibited, so that the rate capability and the cycle performance of the water system zinc ion battery are improved, and the coating has bright application prospect in the field of water system zinc ion batteries.
Drawings
FIG. 1 shows MnO obtained in example 12Physical picture of/rGO hydrogel.
FIG. 2 shows MnO obtained in example 12Physical diagram of/rGO/PANI aerogel.
FIG. 3 shows MnO obtained in example 12/rGO hydrogels (a, c) and MnO2SEM images and scanning element profiles of/rGO/PANI aerogels (b, d).
FIG. 4 is MnO2MnO obtained in example 12/rGO hydrogel and MnO2XRD patterns of/rGO/PANI aerogels.
FIG. 5 shows MnO obtained in example 12/GO hydrogels, MnO2/rGO hydrogel and MnO2Raman spectrum of/rGO/PANI aerogel.
FIG. 6 shows MnO obtained in example 12Infrared spectrum of/rGO/PANI aerogel.
FIG. 7 shows MnO obtained in example 12 Mn 2p high resolution spectrogram of/rGO/PANI aerogel.
FIG. 8 shows MnO obtained in example 12XPS full spectrum (a) of/rGO/PANI aerogel and high resolution spectra (b, C, d) of C, N, O.
FIG. 9 shows MnO obtained in example 12Cyclic Voltammogram (CV) curve of/rGO/PANI aerogel electrode with scan rate of 1mV s-1The scanning voltage is between 0.8V and 1.8V.
FIG. 10 shows MnO obtained in example 12Charge and discharge curves of the/rGO/PANI aerogel electrode under different current densities.
FIG. 11 shows MnO2MnO obtained in example 12/rGO hydrogels, MnO2Rate capability of/rGO/PANI aerogel electrode.
FIG. 12 shows MnO2MnO obtained in example 12/rGO hydrogels, MnO2the/rGO/PANI aerogel electrode is arranged at 1A g-1The following cycle stability test results are shown.
Detailed Description
The technical solution of the present invention is further specifically described below by using specific embodiments and with reference to the accompanying drawings.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Commercial MnO used in the following examples of the invention2Purchased from Shanghai Meixing chemical Co., Ltd.
Example 1
(1) To-be-commercialized MnO2Ball milling was carried out at 400rpm for 24 hours to obtain a particle size of about 2 μm. MnO to be obtained2Graphene oxide (20mL GO, 2mg/mL concentration) in water dispersion was added and mixed by vigorous stirring for 30 minutes to form a homogeneous solution. Then, the homogeneous mixture was transferred to a stainless steel autoclave lined with polytetrafluoroethylene, heated to 150 ℃ and reacted for 6 hours to form cylindrical MnO2A GO hydrogel; the graphene oxide is of a sheet structure, and the transverse dimension of the graphene oxide is 20-30 mu m;
(2) cylindrical MnO2the/GO hydrogel was added to 20mL of deionized water, along with 1.5g Ascorbic Acid (AA) as a reducing agent, and the mixture was transferred to an autoclave and heated at 120 ℃ for 3 hours to reduce GO. Separating and washing with water and ethanol to obtain MnO2The real picture of the/rGO hydrogel is shown in figure 1;
(3) preparation of MnO by Using in situ polymerization Process2/rGO/PANI aerogel:
MnO to be prepared2the/rGO aerogel was placed in 20mL of 0.16M aniline monomer and 1M aqueous HCl and the reaction vessel was kept in an ice bath. To the above solution was then added 20mL of a 1M aqueous HCl solution containing Ammonium Persulfate (APS) in a molar ratio of Ammonium Persulfate (APS) to aniline monomer of 1: 1, polymerization at 0 ℃ for 1 hour. MnO to be obtained2Washing the/rGO/PANI composite material with distilled water for 3-5 times, and drying the washed/rGO/PANI composite material in a vacuum oven at 60 ℃ for 24 hours, wherein the vacuum degree of vacuum drying is-30 kPa to obtain MnO2the/rGO/PANI aerogel has a physical diagram shown in figure 2.
The product produced in this example was characterized as follows:
characterization of MnO by scanning Electron microscope2/rGO hydrogel and MnO2Morphology of/rGO/PANI aerogel, results are shown in FIG. 3Shown in the figure: in FIG. 3a, MnO2the/rGO shows a compact and dense structure, demonstrating MnO2The microspheres are tightly wrapped by the graphene sheet layers and are uniformly distributed in the graphene network. In FIG. 3b, MnO after in situ polymerization of PANI2the/rGO three-dimensional compact assembly is coated by uniform ultrathin shell PANI, MnO2Good retention of original form and structure of/rGO, MnO2the/rGO/PANI still remains highly dense. Furthermore, the elemental distribution plots in FIGS. 3C-d clearly show that Mn, O, C and N are in MnO2/rGO and MnO2Homogeneous distribution over/rGO/PANI. The presence of N element confirms MnO2the/rGO three-dimensional compact assembly is successfully wrapped by PANI.
Further study of crystal structure and MnO was carried out using X-ray diffraction (XRD), Raman spectroscopy, Fourier transform Infrared Spectroscopy (FTIR) and X-ray photoelectron Spectroscopy (XPS)2Composition of/rGO/PANI.
MnO is shown in FIG. 42，MnO2/rGO and MnO2Typical XRD pattern of/rGO/PANI. MnO2/rGO and MnO2/rGO/PANI and MnO2Matched the standard spectra JCPDS 24-0735 corresponding to (101), (111), (211), (220) and (301), respectively, with a broad peak of GO (002) (JCPDS 75-1621) appearing at 26 deg..
The Raman spectra in FIG. 5 further confirm the MnO2Structure of/rGO/PANI at 1351 and 1602cm-1There are two peaks, corresponding to the D and G peaks, respectively. MnO2I of/rGOD/IGA ratio of 0.99, MnO2I of/GOD/IGThe ratio was 0.86, indicating successful chemical reduction of GO. Further characterization of MnO by FTIR2PANI on/rGO three-dimensional dense assemblies.
In FIG. 6, at 1476 and 1557cm-1Peaks at 798, 1118 and 1300cm for quinone vibration with benzene ring and C ═ C, respectively-1And (C) corresponding to stretching vibration of aromatic CH, C ═ N and CN, respectively. MnO2XPS measurement spectrum of/rGO/PANI shows the content of Mn, O, C and N elements. In the Mn 2p spectrum (FIG. 7), two peaks with binding energies of 642.4 and 654.1eV can be assigned to Mn 2p3/2And Mn 2p1/2。
The high resolution C1 s spectrum in fig. 8b shows four distinct peaks corresponding to binding energies of 284.6(C ═ C), 285.5(C-N), 286.2eV (C-O) and 288.6(O-C ═ O). The spectrum of N1 s in FIG. 8c is at 399.5 (-NH), respectively+-) and 401.13 eV (-NH-) show two peaks. In addition, the O1 s spectrum further demonstrates the formation of MnO2。
By using 2M ZnSO4And the zinc foil is used as electrolyte and anode of the zinc ion battery respectively to test electrochemical performance.
FIG. 9 shows MnO2Cyclic Voltammogram (CV) curve of/rGO/PANI electrode with scan rate of 1mV s-1The scanning voltage is between 0.8 and 1.8V. Two pairs of reversible redox peaks, corresponding to MnO, are clearly observed in the figure2Two-step reaction of/rGO/PANI// Zn. .
FIG. 10 shows MnO2the/rGO/PANI/Zn battery is at 0.1A g-1Lower 234.3mAh g-1High initial capacity. Based on the charge and discharge test, a value of 0.1A g is shown in FIG. 11-1To 1A g-1Discharge capacity at different current densities. MnO2The capacity of the/rGO/PANI electrode is 0.1A g-1241.7mAh g can be achieved-1Far above MnO2Capacity of/rGO electrode 178.8mAhg-1And is higher than MnO2Capacity of the electrode 177.4mAh g-1. Even at a current density of 1A g-1In time of MnO2the/rGO/PANI electrode can still provide 115.5mAh g-1High stable capacity of (1), FIG. 12 shows MnO2High rate capability of/rGO/PANI far higher than MnO2Capacity of 84.6mAh g/rGO electrode-1And MnO2Capacity of electrode 80.3mAh g-1. Notably, after 600 cycles, 1A g-1Has 100.6mAh g under the current density-1Further indicates MnO2the/rGO/PANI has excellent long-cycle stability.
Example 2
(1) To-be-commercialized MnO2Prepared by ball milling at 400rpm for 48 hours to obtain a particle size of about 2 μm. MnO to be obtained2Aqueous dispersion with addition of graphene oxide (20mL GO, 50mg/mL concentration)And mixed by vigorous stirring for 60 minutes to form a homogeneous solution. Then, the homogeneous mixture was transferred to a stainless steel autoclave lined with polytetrafluoroethylene, heated to 180 ℃ and reacted for 3 hours to form cylindrical MnO2A GO hydrogel; the graphene oxide is of a sheet structure, and the transverse dimension of the graphene oxide is 20-30 mu m;
(2) cylindrical MnO2the/GO hydrogel was added to 20mL of deionized water along with 1.5g Ascorbic Acid (AA) as a reducing agent, and the mixture was transferred to an autoclave and heated at 100 ℃ for 6 hours to reduce GO. Separating and washing with water and ethanol to obtain MnO2The real picture of the/rGO hydrogel is shown in figure 1;
(3) preparation of MnO by Using in situ polymerization Process2/rGO/PANI aerogel:
MnO to be prepared2the/rGO aerogel was placed in 20mL of 0.12M aniline monomer and 1M aqueous HCl and the reaction vessel was kept in an ice bath. To the above solution was then added 20mL of a 1M aqueous HCl solution containing Ammonium Persulfate (APS) in a molar ratio of Ammonium Persulfate (APS) to aniline monomer of 1: 1, polymerization at 0 ℃ for 1 hour. MnO to be obtained2Washing the/rGO/PANI composite material with distilled water for 3-5 times, and drying the washed/rGO/PANI composite material in a vacuum oven at 60 ℃ for 24 hours, wherein the vacuum degree of vacuum drying is-30 kPa to obtain MnO2a/rGO/PANI aerogel.
Example 3
(1) To-be-commercialized MnO2Ball milling was carried out at 400rpm for 16 hours to obtain a particle size of about 2 μm. MnO to be obtained2Graphene oxide (20mL GO, concentration 0.01mg/mL) in water dispersion was added and mixed by vigorous stirring for 10 minutes to form a homogeneous solution. Then, the homogeneous mixture was transferred to a stainless steel autoclave lined with polytetrafluoroethylene, heated to 120 ℃ and reacted for 6 hours to form cylindrical MnO2A GO hydrogel; the graphene oxide is of a sheet structure, and the transverse dimension of the graphene oxide is 20-30 mu m;
(2) cylindrical MnO2the/GO hydrogel was added to 20mL of deionized water along with 1.5g Ascorbic Acid (AA) as a reducing agent, and the mixture was transferred to an autoclave and heated at 150 ℃ for 3 hours to reduce GO.Separating and washing with water and ethanol to obtain MnO2The real picture of the/rGO hydrogel is shown in figure 1;
(3) preparation of MnO by Using in situ polymerization Process2/rGO/PANI aerogel:
MnO to be prepared2the/rGO aerogel was placed in 20mL of 0.14M aniline monomer and 1M aqueous HCl and the reaction vessel was kept in an ice bath. To the above solution was then added 20mL of a 1M aqueous HCl solution containing Ammonium Persulfate (APS) in a molar ratio of Ammonium Persulfate (APS) to aniline monomer of 1: 1, polymerization at 0 ℃ for 1 hour. MnO to be obtained2Washing the/rGO/PANI composite material with distilled water for 3-5 times, and drying in a vacuum oven at 60 ℃ for 48 hours, wherein the vacuum degree of vacuum drying is-30 kPa to obtain MnO2a/rGO/PANI aerogel.
The product characterization methods of examples 2 and 3 are the same as example 1, and the performances are equivalent, which are not described herein again.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.

Claims (10)

1. MnO (MnO)2The preparation method of the/rGO/PANI aerogel is characterized by comprising the following steps:
(1) uniformly mixing the graphene oxide dispersion liquid and manganese dioxide particles under a closed condition, transferring the mixture into an autoclave, and heating for reaction to obtain MnO2A GO hydrogel;
(2) MnO obtained in the step (1)2Soaking GO hydrogel in deionized water, adding a reducing agent, transferring the mixture into a high-pressure kettle, and heating for reduction reaction to obtain MnO2a/rGO hydrogel;
(3) adding MnO obtained in the step (2) into a mixed aqueous solution containing aniline monomer and hydrochloric acid2Adding mixed aqueous solution of ammonium persulfate and hydrochloric acid into the rGO hydrogel, carrying out polymerization reaction under the ice-water bath condition, washing the obtained sample, and drying in vacuum to obtain MnO2a/rGO/PANI aerogel.
2. The MnO of claim 12The preparation method of the/rGO/PANI aerogel is characterized in that in the step (1), the feeding mass ratio of the manganese dioxide particles to the graphene oxide is (1-10): 1; the average particle size of the manganese dioxide particles is 500 nm-3 mu m; the graphene oxide is of a sheet structure, and the transverse dimension of the graphene oxide is 0.1-100 mu m.
3. The MnO of claim 12The preparation method of the/rGO/PANI aerogel is characterized in that in the step (1), the heating temperature is 120-180 ℃, and the heating time is 3-6 hours.
4. The MnO of claim 12The preparation method of the/rGO/PANI aerogel is characterized in that in the step (1), the concentration of the graphene oxide dispersion liquid is 0.01-50 mg/mL.
5. The MnO of claim 12The preparation method of the/rGO/PANI aerogel is characterized in that in the step (2), the reducing agent is ascorbic acid; the feeding mass ratio of the ascorbic acid to the graphene oxide is (1-10): 1.
6. the MnO of claim 12The preparation method of the/rGO/PANI aerogel is characterized in that in the step (2), the temperature of the heating reduction reaction is 100-150 ℃, and the time is 3-6 hours.
7. The MnO of claim 12The preparation method of the/rGO/PANI aerogel is characterized in that in the step (3), the concentration of the aniline monomer in the mixed aqueous solution containing the aniline monomer and hydrochloric acid is 0.12-0.16M; the concentration of the hydrochloric acid is 0.5-2M.
8. The MnO of claim 12The preparation method of the/rGO/PANI aerogel is characterized in that in the step (3), the mixed water of ammonium persulfate and hydrochloric acidThe concentration of ammonium persulfate in the solution is 0.12-0.16M; the concentration of the hydrochloric acid is 1M.
9. The MnO of claim 12The preparation method of the/rGO/PANI aerogel is characterized in that in the step (3), the temperature of the polymerization reaction is controlled to be 0-4 ℃, and the time of the polymerization reaction is controlled to be 1-2 hours; the temperature is 40-80 ℃, and the time is 24-48 h.
10. MnO obtainable by a process according to any of claims 1 to 92Application of the/rGO/PANI aerogel in an aqueous zinc ion battery.
CN201910755490.9A 2019-08-15 2019-08-15 MnO (MnO)2Preparation method of/rGO/PANI aerogel and application of aerogel in water-based zinc ion battery Pending CN110808359A (en)

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CN112349909A (en) * 2020-11-06 2021-02-09 常州大学 Zinc-ion battery positive electrode composite material and preparation method and application thereof
CN114551845A (en) * 2022-03-02 2022-05-27 成都理工大学 Zinc ion battery with self-charging characteristic and preparation method thereof
CN115360354A (en) * 2022-10-20 2022-11-18 江苏智泰新能源科技有限公司 Preparation method and application of sodium-ion battery positive electrode material

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111871391A (en) * 2020-07-09 2020-11-03 清华大学 Preparation and application of polyvinyl alcohol/graphene oxide/manganese dioxide adsorbent
CN111871391B (en) * 2020-07-09 2022-06-07 清华大学 Preparation and application of polyvinyl alcohol/graphene oxide/manganese dioxide adsorbent
CN112349909A (en) * 2020-11-06 2021-02-09 常州大学 Zinc-ion battery positive electrode composite material and preparation method and application thereof
CN112349909B (en) * 2020-11-06 2022-03-29 常州大学 Zinc-ion battery positive electrode composite material and preparation method and application thereof
CN114551845A (en) * 2022-03-02 2022-05-27 成都理工大学 Zinc ion battery with self-charging characteristic and preparation method thereof
CN115360354A (en) * 2022-10-20 2022-11-18 江苏智泰新能源科技有限公司 Preparation method and application of sodium-ion battery positive electrode material
CN115360354B (en) * 2022-10-20 2023-01-10 江苏智泰新能源科技有限公司 Preparation method and application of sodium-ion battery positive electrode material

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Application publication date: 20200218