CN110797208A - Preparation method and application of electrode material - Google Patents
Preparation method and application of electrode material Download PDFInfo
- Publication number
- CN110797208A CN110797208A CN201911086139.1A CN201911086139A CN110797208A CN 110797208 A CN110797208 A CN 110797208A CN 201911086139 A CN201911086139 A CN 201911086139A CN 110797208 A CN110797208 A CN 110797208A
- Authority
- CN
- China
- Prior art keywords
- disodium
- solution
- metal nitrate
- electrode material
- hydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to the technical field of electrode materials, in particular to a preparation method and application of an electrode material‑And (5) carrying out interlayer diffusion kinetics to obtain the electrode material. According to the description of the embodiment, the electrode material still has high specific capacity of more than or equal to 173F/g under the current density of 150A/g; the method has the advantages of controllable material components, easiness in large-scale production, low cost and the like.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a preparation method and application of an electrode material.
Background
The super capacitor has the advantages of high power density, long cycle life and the like, and is widely applied to the fields of automobiles, electronic devices, high-efficiency utilization of renewable energy sources and the like. However, the energy density of the super capacitor is low, which greatly limits the application range thereof and motivates the research enthusiasm of people for developing super capacitor electrode materials with high energy density. In recent years, researchers have found that transition metal-based materials have a high theoretical energy density and can achieve charge storage and release by undergoing faradaic reactions. However, the charge transfer kinetic process of the material in the Faraday reaction is slow, which can cause the capacity and rate performance to be poor. Therefore, the rate capability of the electrode material can be greatly improved by improving the charge transfer kinetics of the electrode material.
The Layered Double Hydroxide (LDHs) consists of double hydroxide layer plates with positive charges, interlayer anions with negative charges and partial intercalated water molecules, and the general formula is [ M2+ 1-xM3+ x(OH)2]x+[An- x/n]x-·mH2O, wherein M2+Or M3+Represents a divalent radical (e.g. Ni)2+,Mg2+，Co2+，Mn2+，Zn2+Etc.) or trivalent (e.g. Al)3+，Cr3+，Fe3+Etc.) metal ions, An-The anion having a valence of-n, x represents the plate charge density determined by the ratio of divalent to trivalent metal ions (e.g., x ═ M)3+/(M2++M3 +)). In alkaline electrolyte, LDHs performs reversible Faraday reaction (namely reversible transformation between hydroxide and oxyhydroxide) to perform electrochemical energy storage, and has high theoretical specific capacity; the LDHs also has the advantages of simple synthesis, adjustable components, large-scale preparation and the like, is an energy storage material with great potential, and is widely applied to the field of super capacitors.
However, in general, the interlayer spacing of LDHs is small, which is not good for OH in electrochemical energy storage process-Diffusion between the layers limits the extent to which the electrode material participates in the reaction. Therefore, LDHs exhibit poor capacity and rate performance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method and application of an electrode material.
In order to achieve the above purpose, the invention provides the following specific technical scheme:
the invention provides a preparation method of an electrode material, which comprises the following steps:
mixing the intercalation solution and the layered double hydroxide for intercalation reaction to obtain an electrode material;
the intercalation solution is straight chain type disodium dicarboxylate salt solution or conjugated type sodium polycarboxylate solution.
Preferably, the layered double hydroxide is in a flower ball shape formed by mutually cross-connecting double hydroxide nanosheets;
the interlayer spacing of the double-metal hydroxide nanosheets in the layered double-metal hydroxide is 0.8-0.85 nm;
the electrode material is in a flower ball shape formed by cross-connecting double-metal hydroxide nanosheets;
the interlayer spacing of the double-metal hydroxide nanosheets in the electrode material is 0.7-1.3 nm.
Preferably, the concentration of the linear disodium dicarboxylate salt solution or the conjugated sodium polycarboxylate solution is independently (0.08 to 0.12) mol/L.
Preferably, the mass ratio of the solute to the layered double hydroxide in the linear disodium dicarboxylate salt solution or the conjugated sodium polycarboxylate solution is independently (5-40): 1.
Preferably, the linear dicarboxylic acid disodium salt in the linear dicarboxylic acid disodium salt solution is one or more of disodium oxalate, disodium succinate, disodium glutarate, disodium adipate, disodium pimelate, disodium suberate, disodium azelate, disodium sebacate, disodium n-undecanedicarboxylate and disodium n-dodecanedicarboxylate.
Preferably, the conjugated sodium polycarboxylate in the conjugated sodium polycarboxylate solution is one or more of trisodium 1,3, 5-benzenetricarboxylate, tetrasodium 1,2,4, 5-benzenetetracarboxylic acid, disodium 1, 4-terephthalic acid, disodium 1, 4-naphthalenedicarboxylate, disodium 2, 6-naphthalenedicarboxylate, tetrasodium 3,4,9, 10-pyrenetetracarboxylic acid and disodium 4,4' -biphenyldicarboxylate.
Preferably, the temperature of the intercalation reaction is 60-100 ℃, and the time of the intercalation reaction is 12-72 h.
Preferably, the preparation method of the layered double hydroxide comprises the following steps:
mixing a metal nitrate solution, oxalate and a hexamethylenetetramine aqueous solution, and carrying out a precipitation reaction to obtain a layered double hydroxide;
the metal nitrate solution is a divalent metal nitrate solution or a mixed solution of a divalent metal nitrate and a trivalent metal nitrate.
Preferably, when the metal nitrate solution is a mixed solution of a divalent metal nitrate and a trivalent metal nitrate:
the divalent metal in the divalent metal nitrate is Ni2+、Co2+、Mn2+Or Zn2+(ii) a The trivalent metal in the trivalent metal nitrate is Al3+、Cr3+Or Fe3+；
When the metal nitrate solution is a divalent metal nitrate solution:
the divalent metal in the divalent metal nitrate is Ni2+、Co2+、Mn2+And Zn2+Two kinds of (1).
The invention also provides application of the electrode material prepared by the preparation method in the technical scheme as an electrode material.
The invention provides a preparation method of an electrode material, which comprises the following steps: mixing the intercalation solution and the layered double hydroxide for intercalation reaction to obtain an electrode material; the intercalation solution is straight chain type disodium dicarboxylate salt solution or conjugated type sodium polycarboxylate solution. The invention realizes the improvement of OH through increasing the interlayer spacing of the double metal hydroxide nano-sheets by the straight chain type disodium dicarboxylate or the conjugated type sodium polycarboxylate-And (5) carrying out interlayer diffusion kinetics to obtain the electrode material. According to the description of the embodiment, the electrode material still has high specific capacity of more than or equal to 173F/g under the current density of 150A/g. The method has the advantages of controllable material components, easiness in large-scale production, low cost and the like.
Drawings
FIG. 1 is an SEM image of a layered double hydroxide of example 1;
FIG. 2 is an SEM photograph of the electrode material prepared in example 1;
FIG. 3 is XRD patterns of the electrode materials prepared in examples 1 to 7 and the layered double hydroxide prepared in comparative example 1;
FIG. 4 is a graph showing the rate capability of the electrode materials prepared in examples 1 to 7 and the layered double hydroxide prepared in comparative example 1;
FIG. 5 is a graph showing the rate capability of the electrode material prepared in example 6 and the layered double hydroxides prepared in comparative examples 2 to 9.
Detailed Description
The invention provides a preparation method of an electrode material, which comprises the following steps:
mixing the intercalation solution and the layered double hydroxide for intercalation reaction to obtain an electrode material;
the intercalation solution is straight chain type disodium dicarboxylate salt solution or conjugated type sodium polycarboxylate solution.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
Mixing intercalation solution and layered double hydroxide, and carrying out intercalation reaction to obtain an electrode material; the intercalation solution is straight chain type disodium dicarboxylate salt solution or conjugated type sodium polycarboxylate solution.
In the present invention, the concentration of the linear disodium dicarboxylate salt solution or the conjugated sodium polycarboxylate solution is preferably (0.08 to 0.12) mol/L, more preferably (0.09 to 0.11) mol/L, and most preferably 0.10 mol/L; the solvent of the straight chain type dicarboxylic acid disodium salt solution or the conjugated type polycarboxylic acid sodium salt solution is preferably ultrapure water; the linear chain dicarboxylic acid disodium salt in the linear chain dicarboxylic acid disodium salt solution is preferably one or more of disodium oxalate, disodium succinate, disodium glutarate, disodium adipate, disodium pimelate, disodium suberate, disodium azelate, disodium sebacate, disodium n-undecanedicarboxylate and disodium n-dodecanedicarboxylate; when the linear dicarboxylic acid disodium salt is two or more of the above specific choices, the specific components are mixed at any ratio without any particular limitation. The conjugated polycarboxylic acid sodium salt in the conjugated polycarboxylic acid sodium salt solution is preferably one or more of 1,3, 5-benzene tricarboxylic acid trisodium, 1,2,4, 5-benzene tetracarboxylic acid tetrasodium, 1, 4-terephthalic acid disodium, 1, 4-naphthalene dicarboxylic acid disodium, 2, 6-naphthalene dicarboxylic acid disodium, 3,4,9, 10-pyrenetetracarboxylic acid tetrasodium and 4,4' -biphenyl dicarboxylic acid disodium; when the conjugate type polycarboxylic acid sodium salt is two or more of the above specific choices, the specific ratio of the specific substances is not particularly limited, and the specific substances may be mixed in any ratio.
In the invention, the layered double hydroxide is formed by mutually cross-connecting double hydroxide nanosheets (as shown in fig. 1), and the interlayer spacing of the double hydroxide nanosheets in the layered double hydroxide is preferably 0.8-0.85 nm, more preferably 0.81-0.84 nm, and most preferably 0.82 nm. The interlayer anion in the layered double hydroxide is preferably a nitrate ion.
In the present invention, the layered double hydroxide is preferably prepared by a preparation method comprising the steps of:
mixing a metal nitrate solution and an aqueous solution containing oxalate and hexamethylenetetramine, and carrying out a precipitation reaction to obtain a layered double hydroxide;
the metal nitrate solution is a mixed solution of divalent metal nitrate and trivalent metal nitrate or a divalent metal nitrate solution.
In the present invention, the solvent of the metal nitrate solution is preferably ultrapure water; when the metal nitrate solution is a mixed solution of a divalent metal nitrate and a trivalent metal nitrate: the divalent metal in the divalent metal nitrate is preferably Ni2+、Co2+、Mn2+Or Zn2+(ii) a The trivalent metal in the trivalent metal nitrate is preferably Al3+、Cr3+Or Fe3+(ii) a The molar ratio of the divalent metal nitrate to the trivalent metal nitrate is preferably (0.14-7): 1, more preferably (2 to 7): 1, most preferably 3: 1; the concentration of the divalent metal nitrate in the metal nitrate solution is preferably 0.03-0.22 mol/L, more preferably 0.1-0.17 mol/L, and most preferably 0.15 mol/L.
When the metal nitrate solution is a divalent metal nitrate solution: the divalent metal in the divalent metal nitrate is preferably Ni2+、Co2+、Mn2+And Zn2+Two kinds of (1). In the invention, the molar ratio of the two divalent metal nitrates is preferably (0.1-19): 1, more preferably (5-9): 1, most preferably 7: 1; the total concentration of the divalent metal nitrate in the divalent metal nitrate solution is preferably 0.05-0.4 mol/L, more preferably 0.1-0.3 mol/L, and most preferably 0.25 mol/L.
In the invention, the concentration of the hexamethylenetetramine in the aqueous solution containing oxalate and hexamethylenetetramine is preferably (0.8-1.2) mol/L, and more preferably 1.0 mol/L; the concentration of the sodium oxalate in the aqueous solution of the oxalate and the hexamethylenetetramine is preferably (4.5-5.5) g/L, and more preferably 5.0 g/L.
In the invention, the dosage ratio of the metal nitrate solution and the aqueous solution containing oxalate and hexamethylenetetramine is preferably (75-85) mL: (15-25) mL, more preferably 80 mL: 20 mL.
In the present invention, the specific process of mixing the metal nitrate solution and the aqueous solution containing oxalate and hexamethylenetetramine is preferably: and degassing and oxygenating the metal nitrate solution, heating the solution to 40-60 ℃ under the stirring condition, and quickly adding the degassed aqueous solution dissolved with sodium oxalate and hexamethylenetetramine.
In the present invention, the oxalate salt is preferably a soluble oxalate salt, more preferably sodium oxalate or potassium oxalate; in the present invention, the oxalate functions to provide oxalate, and the oxalate and metal ions generate oxalate insoluble in water; the oxalate can be used as a nucleation center for LDH nanosheet self-assembly during precipitation reaction, and finally grows to form LDHs (product 1) with a flower-ball-shaped appearance. If oxalic acid is not added, the generated nanosheets are usually distributed in a disordered manner, and the flower-ball-shaped morphology is difficult to obtain. The hexamethylene tetramine is slowly hydrolyzed in water to generate hydroxide ions, and the hydroxide ions react with metal ions to generate layered double hydroxides.
In the present invention, the precipitation reaction is preferably carried out under stirring, and the stirring is not particularly limited; the temperature of the precipitation reaction is preferably 95-100 ℃, and more preferably 96-98 ℃; the time of the precipitation reaction is preferably 4-12 hours, and more preferably 6-8 hours.
After the precipitation reaction is finished, the invention preferably carries out post-treatment on the product obtained by the precipitation reaction, wherein the post-treatment is preferably filtration, washing and drying; the invention does not have any special limitation on the filtration, and the filtration process known by the technicians in the field is adopted; in the present invention, the washing is preferably carried out by sufficiently washing with ultrapure water and anhydrous ethanol in this order; the drying process is not particularly limited, and may be performed by a drying process known to those skilled in the art.
In the present invention, the mixing of the intercalation solution and the layered double hydroxide is preferably carried out by adding the layered double hydroxide to the intercalation solution.
In the present invention, the mass ratio of the solute to the layered double hydroxide in the linear disodium dicarboxylate salt solution or the conjugated sodium polycarboxylate solution is preferably (5 to 40):1, more preferably (10 to 30): 1, most preferably (15-25): 1.
in the invention, the temperature of the intercalation reaction is preferably 60-100 ℃, and more preferably 70-80 ℃; the time of the intercalation reaction is preferably 12-72 h, more preferably 20-60 h, and most preferably 30-50 h.
After the intercalation reaction is finished, the invention preferably carries out post-treatment on a product system obtained after the reaction is finished; the post-treatment preferably comprises cooling, filtering, washing and vacuum drying which are carried out in sequence; the cooling and filtering method is not limited in any way, and the cooling and filtering process known to those skilled in the art can be adopted; in the present invention, the washing is preferably carried out by fully washing with ultrapure water and absolute ethyl alcohol in this order; in the invention, the temperature of the vacuum drying is preferably 75-85 ℃, more preferably 80 ℃, and the time of the vacuum drying is preferably 10-15 h, more preferably 12 h.
In the invention, the linear chain dicarboxylic acid disodium salt or the conjugated polycarboxylic acid sodium salt can realize the regulation and control of the conductivity and the interlayer spacing of the bimetallic hydroxide nanosheet, and carboxylate ions are utilized to replace NO between the layers of the layered bimetallic hydroxide material3-Ions, thereby achieving the purpose of regulating and controlling the interlayer spacing. Due to the size differences of the different carboxylate ions, the interlayer spacing of the final electrode material is also different.
In the invention, the electrode material is formed by cross-linking of double-metal hydroxide nanosheets;
the interlayer spacing of the double-metal hydroxide nanosheets in the electrode material is preferably 0.7-1.3 nm.
The invention also provides application of the electrode material prepared by the preparation method in the technical scheme as an electrode material.
The following examples are provided to illustrate the preparation and application of the electrode material of the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Providing Ni (NO)3)2·6H2O and Co (NO)3)2·6H2Mixed solution of O (Ni (NO)3)2·6H2O is 17.5mmol, Co (NO)3)2·6H22.5mmol of O and 80mL of ultrapure water), an aqueous solution of sodium oxalate and hexamethylenetetramine (0.1 g of sodium oxalate, 20mmol of hexamethylenetetramine and 20mL of water) and a disodium succinate solution (10 mmol of disodium succinate and 100mL of ultrapure water);
mixing Ni (NO)3)2·6H2O and Co (NO)3)2·6H2Degassing O mixed solution, oxygenating, heating to 40 deg.C under stirring, and rapidly addingAdding degassed sodium oxalate and hexamethylenetetramine aqueous solution, performing precipitation reaction (95 ℃ and 6 hours) under the stirring condition, cooling, filtering, fully washing with ultrapure water and absolute ethyl alcohol, and drying to obtain layered double hydroxide;
the layered double hydroxide is subjected to SEM test, the test result is shown in figure 1, and the interlayer spacing of the layered double hydroxide is 0.82nm as can be seen from figure 1;
mixing 100mg of the layered double hydroxide with a disodium succinate solution, degassing and oxygenating, carrying out intercalation reaction (at 90 ℃ for 24 hours), cooling, filtering, fully washing with ultrapure water and absolute ethyl alcohol, and carrying out vacuum drying (at 80 ℃ for 12 hours) to obtain an electrode material;
the electrode material was subjected to SEM test, and the test result is shown in fig. 2, and as can be seen from fig. 2, the interlayer distance of the double metal hydroxide was 0.88 nm.
Example 2
The preparation method is referred to example 1 except that disodium succinate in example 1 is replaced with disodium adipate; the interlayer spacing of the double metal hydroxide in the electrode material is 0.95 nm.
Example 3
The preparation method is referred to example 1 except that disodium succinate in example 1 is replaced with disodium sebacate; the interlayer spacing of the double metal hydroxide in the electrode material is 1.02-1.29 nm.
Example 4
The preparation method is referred to example 1 except that trisodium 1,3, 5-benzenetricarboxylate is used instead of disodium succinate in example 1; the interlayer spacing of the double metal hydroxide in the electrode material was 0.82 nm.
Example 5
The preparation method is referred to example 1 except that disodium 2, 6-naphthalenedicarboxylate is used instead of disodium succinate in example 1; the interlayer spacing of the double metal hydroxide in the electrode material was 0.84 nm.
Example 6
The preparation method is referred to example 1 except that disodium succinate in example 1 is replaced with disodium 1, 4-terephthalate; the interlayer spacing of the double metal hydroxide in the electrode material is 0.91 nm.
Example 7
The preparation method is as described in example 1 except that disodium succinate in example 1 is replaced with tetrasodium 3,4,9, 10-pyrenetetracarboxylic acid; the interlayer spacing of the double metal hydroxide in the electrode material is 0.94 nm.
Comparative example 1
The preparation method is referred to example 1 except that sodium carbonate is used instead of disodium succinate in example 1; the interlayer spacing of the double hydroxide in the layered double hydroxide is 0.765 nm.
Comparative examples 2 to 9
Comparative example 2 is a hollow Ni-Al LDH microsphere: the preparation method is referred to chem. mater, 2012,24, 1192-1197;
comparative example 3 is Ni-Co-Al LDH: the preparation method refers to electrochim. acta,2017,225, 263-containing 271;
comparative example 4 is Co-Al LDH/graphene: the preparation method is described in adv.funct.mater, 2015,25, 1648-1655;
comparative example 5 is Co-Ni LDH/PEDOT PSS: the preparation method is referred to adv.funct.mater, 2015,25, 2745-;
comparative example 6 is Ni-Fe LDH: the preparation method refers to J.Power Sources,2016,325, 675-681;
comparative example 7 is Ni-Co-Al LDH NPs/Ni-Co CH NWs: the preparation method is described in adv. energy mate, 2014,4,1400761;
comparative example 8 is C/Ni-Co LDH/Co9S8: the preparation method is referred to adv.mater, 2017,29, 1606814;
comparative example 9 is Ni-Co-Al LDH: the preparation method is referred to adv. energy mate, 2014,4, 1301240.
Test example
XRD tests are carried out on the electrode materials prepared in examples 1-7 and the layered double hydroxide prepared in comparative example 1, and the test result is shown in figure 3, and it can be known from figure 3 that the interlayer spacing of the double hydroxide in the electrode material is 0.7-1.3 nm.
The electrode materials prepared in examples 1 to 7 and the layered double hydroxides prepared in comparative examples 1 to 9 are subjected to a rate performance test in a 6M KOH electrolyte, and the test results are shown in FIG. 4 and FIG. 5 (FIG. 4 is a rate performance curve of the products obtained in examples 1 to 7 and comparative example 1; FIG. 5 is a rate performance curve of the products obtained in examples 6 and comparative examples 2 to 9), and according to FIG. 4, specific capacities of the products obtained in examples 1 to 7 and comparative example 1 at different current densities are summarized in Table 1:
TABLE 1 specific capacities of the products obtained in examples 1 to 7 and comparative example 1 at different current densities
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Comparative example 1 | |
| 1A/g | 1653F/g | 1844F/g | 1372F/g | 1841F/g | 1869F/g | 2115F/g | 1631F/g | 1605F/g |
| 50A/g | 590F/g | 751F/g | 494F/g | 819F/g | 923F/g | 949F/g | 760F/g | 456F/g |
| 100A/g | 359F/g | 430F/g | 294F/g | 492F/g | 600F/g | 626F/g | 413F/g | 23.9F/g |
| 150A/g | 205F/g | 255F/g | 173F/g | 273F/g | 389F/g | 410F/g | 220F/g | 1.05F/g |
As can be seen from FIG. 5, the product prepared by the preparation method of the present invention has high rate energy storage performance compared with the prior art.
As can be seen from the above examples, the electrode material provided by the invention still has a high specific capacity of more than or equal to 173F/g at a current density of 150A/g.
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 (10)
1. The preparation method of the electrode material is characterized by comprising the following steps of:
mixing the intercalation solution and the layered double hydroxide for intercalation reaction to obtain an electrode material;
the intercalation solution is straight chain type disodium dicarboxylate salt solution or conjugated type sodium polycarboxylate solution.
2. The method of claim 1, wherein the layered double hydroxide is in the shape of flower spheres cross-linked by double hydroxide nanosheets;
the interlayer spacing of the double-metal hydroxide nanosheets in the layered double-metal hydroxide is 0.8-0.85 nm;
the electrode material is in a flower ball shape formed by cross-connecting double-metal hydroxide nanosheets;
the interlayer spacing of the double-metal hydroxide nanosheets in the electrode material is 0.7-1.3 nm.
3. The method according to claim 1, wherein the concentration of the linear type disodium dicarboxylate salt solution or the conjugated type sodium polycarboxylate solution is independently (0.08 to 0.12) mol/L.
4. The method according to claim 1 or 3, wherein the mass ratio of the solute to the layered double hydroxide in the linear disodium dicarboxylate salt solution or the conjugated sodium polycarboxylate solution is independently (5 to 40): 1.
5. The method according to claim 4, wherein the disodium salt of a linear dicarboxylic acid in the disodium salt solution of a linear dicarboxylic acid is one or more of disodium oxalate, disodium succinate, disodium glutarate, disodium adipate, disodium pimelate, disodium suberate, disodium azelate, disodium sebacate, disodium n-undecanedicarboxylate, and disodium n-dodecanedicarboxylate.
6. The method according to claim 4, wherein the conjugated sodium polycarboxylate in the conjugated sodium polycarboxylate solution is one or more selected from the group consisting of trisodium 1,3, 5-benzenetricarboxylate, tetrasodium 1,2,4, 5-benzenetetracarboxylic acid, disodium 1, 4-terephthalic acid, disodium 1, 4-naphthalenedicarboxylate, disodium 2, 6-naphthalenedicarboxylate, tetrasodium 3,4,9, 10-pyrenetetracarboxylic acid, and disodium 4,4' -biphenyldicarboxylate.
7. The preparation method according to claim 1, wherein the temperature of the intercalation reaction is 60 to 100 ℃ and the time of the intercalation reaction is 12 to 72 hours.
8. The method of claim 1, wherein the layered double hydroxide is prepared by a method comprising the steps of:
mixing a metal nitrate solution, oxalate and a hexamethylenetetramine aqueous solution, and carrying out a precipitation reaction to obtain a layered double hydroxide;
the metal nitrate solution is a divalent metal nitrate solution or a mixed solution of a divalent metal nitrate and a trivalent metal nitrate.
9. The production method according to claim 8, wherein when the metal nitrate solution is a mixed solution of a divalent metal nitrate and a trivalent metal nitrate:
the divalent metal in the divalent metal nitrate is Ni2+、Co2+、Mn2+Or Zn2+(ii) a The trivalent metal in the trivalent metal nitrate is Al3+、Cr3+Or Fe3+；
When the metal nitrate solution is a divalent metal nitrate solution:
the divalent metal in the divalent metal nitrate is Ni2+、Co2+、Mn2+And Zn2+Two kinds of (1).
10. The electrode material prepared by the preparation method of any one of claims 1 to 9 is used as an electrode material in electrochemistry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911086139.1A CN110797208B (en) | 2019-11-08 | 2019-11-08 | Preparation method and application of electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911086139.1A CN110797208B (en) | 2019-11-08 | 2019-11-08 | Preparation method and application of electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110797208A true CN110797208A (en) | 2020-02-14 |
| CN110797208B CN110797208B (en) | 2020-12-22 |
Family
ID=69443313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911086139.1A Active CN110797208B (en) | 2019-11-08 | 2019-11-08 | Preparation method and application of electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110797208B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056827A (en) * | 1990-05-25 | 1991-12-11 | 密歇根州州立大学托管委员会 | The multiple hydroxide of the stratiform that the polyacid root embeds |
| US5728366A (en) * | 1994-04-29 | 1998-03-17 | Aluminum Company Of America | Two powder synthesis of hydrotalcite and hydrotalcite-like compounds with monovalent organic anions |
| CN102796280A (en) * | 2012-08-29 | 2012-11-28 | 北京化工大学 | Supramolecular intercalated structure polymer antioxidant |
| CN104779059A (en) * | 2015-04-16 | 2015-07-15 | 电子科技大学 | Supercapacitor using nickel aluminum hydrotalcite nanometer material as anode material |
| CN108428904A (en) * | 2018-04-04 | 2018-08-21 | 北京航空航天大学 | One kind hydrotalcite oxygen reduction catalyst of silver-based containing cerium and the preparation method and application thereof |
-
2019
- 2019-11-08 CN CN201911086139.1A patent/CN110797208B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056827A (en) * | 1990-05-25 | 1991-12-11 | 密歇根州州立大学托管委员会 | The multiple hydroxide of the stratiform that the polyacid root embeds |
| US5728366A (en) * | 1994-04-29 | 1998-03-17 | Aluminum Company Of America | Two powder synthesis of hydrotalcite and hydrotalcite-like compounds with monovalent organic anions |
| CN102796280A (en) * | 2012-08-29 | 2012-11-28 | 北京化工大学 | Supramolecular intercalated structure polymer antioxidant |
| CN104779059A (en) * | 2015-04-16 | 2015-07-15 | 电子科技大学 | Supercapacitor using nickel aluminum hydrotalcite nanometer material as anode material |
| CN108428904A (en) * | 2018-04-04 | 2018-08-21 | 北京航空航天大学 | One kind hydrotalcite oxygen reduction catalyst of silver-based containing cerium and the preparation method and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| 宋延超: "水滑石及其复合物的合成与电容性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 李贺军 等: "《先进复合材料学》", 31 December 2016, 西北工业大学出版社 * |
| 杜宝中 等: "有机酸阴离子_LDH复合材料的插层组装条件及热稳定性研究", 《材料导报》 * |
| 路璐 等: "芳香羧酸阴离子插层水滑石的合成和紫外性能研究", 《四川理工学院学报（自然科学版）》 * |
| 郑德 等: "《稳定剂》", 30 June 2011, 国防工业出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110797208B (en) | 2020-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109225233B (en) | Layered double metal hydroxide/carbon quantum dot electrocatalyst and preparation method thereof | |
| CN101752564B (en) | Hydrothermal synthesis method of LiFePO4 of anode material of lithium ion battery with one-dimensional nanometer structure | |
| CN113517143B (en) | Composite electrode material and preparation method and application thereof | |
| CN109354056B (en) | Iron-doped copper sulfide nanosheet material with abundant defects and preparation method and application thereof | |
| CN109289857B (en) | Rare earth element doped layered composite metal hydroxide and preparation and application thereof | |
| CN110639565A (en) | Carbon-bimetal phosphide composite material and preparation method thereof | |
| CN111185201B (en) | Rhenium-doped molybdenum sulfide nanosheet/carbon cloth composite material, preparation method thereof and application thereof in hydrogen production by electrocatalysis of water | |
| CN1890183A (en) | Process for making nickel hydroxide | |
| CN114084940B (en) | Active material, adsorption electrode, capacitive deionization device, preparation method and application | |
| CN113753963B (en) | Tin cobalt disulfide nano-particles and preparation method and application thereof | |
| Hu et al. | Ternary layered double hydroxide cathode materials for electrochemical energy storage: a review and perspective | |
| CN113621988B (en) | High-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst and preparation method and application thereof | |
| CN112723425B (en) | Ultrathin nanometer flower-structure hydrotalcite supercapacitor electrode material and preparation method thereof | |
| CN113151854B (en) | Multi-metal non-oxide electrocatalyst and preparation method and application thereof | |
| CN110797208B (en) | Preparation method and application of electrode material | |
| CN109119251B (en) | Porous MnCo2O4．5Preparation method of electrode material | |
| CN114933292B (en) | Preparation method and application of lithium iron phosphate | |
| CN108428904B (en) | Cerium-silver-containing hydrotalcite oxygen reduction catalyst and preparation method and application thereof | |
| CN116334649A (en) | Preparation method and application of alkyl lithium modified layered double hydroxide catalyst | |
| CN113754894B (en) | Asymmetric coordination double-site metal organic framework nano material and preparation method and application thereof | |
| CN112427043B (en) | Transition metal compound nanosheet and preparation method and application thereof | |
| CN115579249A (en) | Supercapacitor electrode material CNT @ M-Ni-OH and preparation method and application thereof | |
| CN111994965B (en) | Preparation method of precursor of LTH-structure ternary cathode material | |
| CN114988481A (en) | Sodium ion battery positive electrode material precursor and preparation method thereof | |
| CN106784825A (en) | A kind of spherical nickeliferous carbonic acid manganese material and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |