CN108314092A - A kind of foamed nickel supported nano bar-shape cobalt molybdate and its preparation method and application - Google Patents
A kind of foamed nickel supported nano bar-shape cobalt molybdate and its preparation method and application Download PDFInfo
- Publication number
- CN108314092A CN108314092A CN201711481258.8A CN201711481258A CN108314092A CN 108314092 A CN108314092 A CN 108314092A CN 201711481258 A CN201711481258 A CN 201711481258A CN 108314092 A CN108314092 A CN 108314092A
- Authority
- CN
- China
- Prior art keywords
- molybdate
- cobalt
- preparation
- nano bar
- shape
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of foamed nickel supported nano bar-shape cobalt molybdates and its preparation method and application.The preparation method of the foamed nickel supported nano bar-shape cobalt molybdate includes:The cleaning step of nickel foam;The preparation process of reaction solution:Molybdate and cobalt salt difference is soluble in water, after stirring and dissolving, obtain molybdate solution and cobalt salt solution;Then molybdate solution is added drop-wise in cobalt salt solution, it is lasting to stir, obtain uniformly mixed reaction solution;Hydrothermal treatment step;And the processing step of hydrothermal product.The present invention is effectively improved the electric conductivity of cobalt molybdate using the method for hydrothermal synthesis in foam nickel surface growing nano-rod shape cobalt molybdate;Uniform nano bar-shape structure shortens the insertion distance of lithium ion;The material is used for lithium ion battery negative material, can effectively improve its electric conductivity and high rate performance etc.;In addition, the present invention has many advantages, such as that preparation process is simple and convenient to operate, to reappear performance good.
Description
Technical field
The present invention relates to a kind of foamed nickel supported nano bar-shape cobalt molybdates and its preparation method and application, belong to inorganic material
Synthesis field and its application in electrochemical field.
Background technology
Negative material of the transition metal oxide as lithium ion battery, with its high theoretical capacity and energy density, excellent
Different cycle life and high rate performance, abundant mineral resources and easy preparation process etc. are expected to replace traditional carbon-based negative
Pole material.However in charge and discharge process, along with the insertion and deintercalation of lithium ion, alloy and removal alloying, oxidation and reduction
Reaction etc., inevitably damages its structure, caving in the powdered of active material for structure etc. occurs, leads to battery
Internal resistance increase, capacity attenuation and cycle life the harmful effects such as reduce.
The binary or multi-element transition metal oxides that carrier grows nanostructure are done using conductive matrices.Special combination knot
Structure and nano-scale being capable of many-sided chemical properties for improving transition metal oxide.(1) carrier is done using conductive matrices, it can
To enhance the electric conductivity of transition metal oxide, it is not required to add any conductive agent again;(2) binary or polynary transiting metal oxidation
Object.On the one hand, due to synergistic effect, each transition metal element has the different coefficients of expansion that can alleviate knot during storing up lithium
The expansion of structure;On the other hand, the mixing of binary or the simple oxide in the non-traditional meaning of multi-element transition metal oxides is answered
With more lithiums alloying reaction can occur for miscellaneous chemical constitution, improve capacity;In addition binary or polynary transiting metal oxidation
Object is shown compared with the higher electric conductivity of single oxide;(3) nanostructure, high specific surface area, can improve active material with
The contact area of electrolyte provides more active sites, while can also shorten the intercalation/deintercalation distance of lithium ion, improves
Chemical property etc..
(" the Porous Iron Cobaltate Nanoneedles Array on Nickel Foam such as nearest Wang Yu
as Anode Materials for Lithium-ion Batteries with Enhanced Electrochemical
Performance ", ACS Appl.Mater.Interfaces, 2016,8 (2), pp 1351-1359), it is moved back using water hot-hot
The cobalt acid that fiery two-step method is successfully prepared foamed nickel supported nanometer needle construction is ferrous, after tested:In 0.01-3V, the electricity of 100mA/g
Under current density, there is 1962mAhg-1Reversible specific capacity (coulombic efficiency 92-95%);Under the current density of 2000mA/g, have
875mAh g-1Specific discharge capacity, show excellent high rate performance.Cobalt molybdate be a kind of potentiality are larger in molybdate lithium from
Sub- cell negative electrode material, searching document are understood:Foamed nickel supported cobalt molybdate as lithium ion battery negative material report not yet
It announces, is all to be reported as the positive electrode of ultracapacitor at present, such as:GK Veerasubramani,Improved
electrochemical performances of binder-free CoMoO 4 nanoplate arrays@Ni foam
Electrode using redox additive electrolyte, Journal of Power Sources, 2016,306:
378-386., Z Zhang etc., Formation of hierarchical CoMoO4@MnO2 core-shell nanosheet
Arrays on nickel foam with markedly enhanced pseudocapacitive properties,
Journal of Power Sources,2015,296:104752071 A of 162-168. and Chinese patent CN.It is special at this
In profit, we use the method for hydrothermal synthesis to be successfully prepared foamed nickel supported nano bar-shape cobalt molybdate for the first time, and for lithium from
Sub- cell negative electrode material.
Invention content
The present invention provides a kind of foamed nickel supported nano bar-shape cobalt molybdate, while the present invention also provides above-mentioned foamed nickel supported
The preparation method and application of nano bar-shape cobalt molybdate.
To achieve the above object, the present invention uses following technical scheme:
A kind of preparation method of foamed nickel supported nano bar-shape cobalt molybdate, includes the following steps:
The cleaning step of nickel foam;
The preparation process of reaction solution:Molybdate and cobalt salt difference is soluble in water, after stirring and dissolving, respectively obtain molybdic acid
Salting liquid and cobalt salt solution;Then the molybdate solution is added drop-wise in the cobalt salt solution, it is lasting to stir, it is equal to obtain mixing
Even reaction solution;
Hydrothermal treatment step:The reaction solution is transferred in reaction kettle, and places the nickel foam after cleaning, closed
Hydro-thermal process is carried out under environment, obtains hydrothermal product;
The processing step of hydrothermal product:The hydrothermal product is naturally cooled into room temperature, cleaned, drying process obtains
The foamed nickel supported nano bar-shape cobalt molybdate.
The present invention be molybdate is reacted with cobalt salt solution under conditions of high pressure-temperature to generate nano bar-shape cobalt molybdate, and
It is carried on above nickel foam.
In above-mentioned preparation method, as a preferred implementation manner, in the cleaning step of the nickel foam, nickel foam is taken
It is sequentially placed into ethyl alcohol, deionized water, hydrochloric acid, acetone, ethyl alcohol, deionized water and is cleaned by ultrasonic, the nickel foam after being cleaned;It should
Cleaning step can very well remove the various impurity being adsorbed in nickel foam, to obtain the higher nickel foam of purity, so as to
Improve the performance of final products.Preferably, the hydrochloric acid a concentration of 0.5-1mol/L (such as 0.55mol/L, 0.6mol/L,
0.7mol/L、0.8mol/L、0.9mol/L、0.98mol/L);The time of each ultrasonic cleaning be 10-20min (such as
11min, 12min, 13min, 14min, 15min, 17min, 18min, 19min), power 2-5Kw.
It is described to hold as a preferred implementation manner, in the preparation process of the reaction solution in above-mentioned preparation method
Continuous stirring refers to persistently being stirred when molybdate solution is added dropwise;Preferably, the time persistently stirred be 8-15min (such as
9min、12min、13min、14min)。
In above-mentioned preparation method, as a preferred implementation manner, in the preparation process of the reaction solution, the molybdenum
Hydrochlorate is sodium molybdate or ammonium molybdate;The cobalt salt is cobalt acetate or cobalt nitrate.
It is described anti-as a preferred implementation manner, in the preparation process of the reaction solution in above-mentioned preparation method
It is 1-1.6 to answer the molar ratio of molybdenum and cobalt in the cobalt salt in the molybdate in liquid:1 (such as 1.05:1、1.1:1、1.2:1、
1.3:1、1.4:1、1.45:1), more preferably 1-1.2:1 (such as 1.02:1、1.05:1、1.08:1、1.12:1、1.15:1、
1.18:1)。
In above-mentioned preparation method, as a preferred implementation manner, in the reaction solution, molybdenum concentration 5-20mmol/L
(such as 6mmol/L, 8mmol/L, 10mmol/L, 12mmol/L, 14mmol/L, 16mmol/L, 18mmol/L).
In above-mentioned preparation method, as a preferred implementation manner, in the hydrothermal treatment step, the nickel foam
Quality and molybdate and the ratio of cobalt salt gross mass are 2:1-10:1 (such as 3:1、4:1、5:1、6:1、7:1、8:1、9:1).
In above-mentioned preparation method, as a preferred implementation manner, in the hydrothermal treatment step, the hydro-thermal process
Mode of heating be electrical heating or microwave heating.
In above-mentioned preparation method, as a preferred implementation manner, in the hydrothermal treatment step, the hydro-thermal process
Temperature be 140-200 DEG C (such as 142 DEG C, 144 DEG C, 146 DEG C, 155 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 188 DEG C, 192 DEG C,
195 DEG C, 198 DEG C), soaking time be 2-24h (such as 2.5h, 3h, 5h, 8h, 12h, 15h, 18h, 20h, 22h, 23h,
23.5h);It is highly preferred that the temperature of the hydro-thermal process be 170-190 DEG C (such as 172 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 188
DEG C), soaking time is 6-10h (such as 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h).
It is described clear as a preferred implementation manner, in the processing step of the hydrothermal product in above-mentioned preparation method
It refers to alternately being cleaned with water, ethyl alcohol to wash, and is amounted to six times.
It is described dry as a preferred implementation manner, in the processing step of the hydrothermal product in above-mentioned preparation method
The temperature of dry processing be 50-180 DEG C (such as 52 DEG C, 54 DEG C, 60 DEG C, 70 DEG C, 90 DEG C, 110 DEG C, 130 DEG C, 140 DEG C, 145 DEG C,
148 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 178 DEG C), soaking time be 6-15h (such as 6.5h, 7h, 8h, 9h, 10h, 11h, 12h,
13h、14h、14.5h);It is highly preferred that the temperature of the drying process be 70-90 DEG C (such as 72 DEG C, 75 DEG C, 80 DEG C, 85 DEG C,
88 DEG C), soaking time is 8-12h (such as 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h).
A kind of foamed nickel supported nano bar-shape cobalt molybdate prepared using the above method, the uniform nano bar-shape molybdic acid of pattern
Cobalt is equably covered in foam nickel surface, and the size for the nano bar-shape cobalt molybdate being carried in the nickel foam is:Nanometer rods are straight
Diameter is 60-80 nanometers, and length is 200-300 nanometers.
Application of the foamed nickel supported nano bar-shape cobalt molybdate as negative material in lithium ion battery.
Compared with prior art, the beneficial effects of the invention are as follows:
1) present invention is effectively improved using the method for hydrothermal synthesis in foam nickel surface growing nano-rod shape cobalt molybdate
The electric conductivity of cobalt molybdate;Uniform nano bar-shape structure shortens the insertion distance of lithium ion;The material is used for lithium-ion electric
Pond negative material can effectively improve its electric conductivity and high rate performance etc.;
2) present invention has many advantages, such as that preparation process is simple and convenient to operate, to reappear performance good.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is this hair
Some bright embodiments for those of ordinary skill in the art without having to pay creative labor, can be with
Obtain other attached drawings according to these attached drawings.
Fig. 1 is X-ray diffraction (XRD) figure of foamed nickel supported nano bar-shape cobalt molybdate prepared by the embodiment of the present invention 1.
Fig. 2 is that the scanning electron microscope (SEM) of the foamed nickel supported nano bar-shape cobalt molybdate of the embodiment of the present invention 1 is shone
Piece, wherein (a) is foamed nickel supported nano bar-shape cobalt molybdate low power SEM, it is (b) foamed nickel supported nano bar-shape cobalt molybdate high power
SEM。
Fig. 3 is electric using the experiment that foamed nickel supported nano bar-shape cobalt molybdate is assembled as raw material prepared by the embodiment of the present invention 1
CV curve graph of the pond at 0.01-3.0V.
Fig. 4 is electric using the experiment that foamed nickel supported nano bar-shape cobalt molybdate is assembled as raw material prepared by the embodiment of the present invention 1
Capacitance-voltage curves figure of the pond at 0.01-3.0V.
Fig. 5 is electric using the experiment that foamed nickel supported nano bar-shape cobalt molybdate is assembled as raw material prepared by the embodiment of the present invention 1
Capacity (coulombic efficiency)-cyclic curve figure of the pond at 0.01-3.0V.
Fig. 6 is with capacity-of the foamed nickel supported nano bar-shape cobalt molybdate under different electric currents prepared by the embodiment of the present invention 1
Cyclic curve figure.
Specific implementation mode
Present disclosure will be described in further detail by embodiment combination attached drawing below, protection of the invention
Range is including but not limited to following each embodiments.
Specific experiment step or condition person are not specified in embodiment, according to routine experiment described in document in the art
The operation of step or condition can carry out.The various reagents and raw material used in embodiment are commercial product.
Embodiment 1
The present embodiment prepares foamed nickel supported nano bar-shape cobalt molybdate by hydro-thermal method.
Preparation method includes the following steps:
(1) cleaning of nickel foam:It is 250um or so, small pieces (1cm to take aperture2) nickel foam, be sequentially placed into 5ml ethyl alcohol,
In 5ml deionized waters, 5ml 1mol/L hydrochloric acid, 5ml acetone, 5ml ethyl alcohol, 5ml deionized waters, the ultrasonic cleaning in each cleaning solution
Time is 10min, ultrasonic power 3KW;
(2) preparation of reaction solution:Bis- molybdic acid hydrate sodium (0.7mmol) of 0.1694g is weighed respectively and 0.2037g six is hydrated
Cobalt nitrate (0.7mmol) is respectively dissolved in 35ml deionized waters, after stirring and dissolving, obtains sodium molybdate solution and cobalt nitrate solution;So
Sodium molybdate solution is added drop-wise in cobalt nitrate solution afterwards, and is stirred when being added dropwise, continues 10min, obtains uniformly mixed reaction
Liquid;
(3) hydrothermal treatment step:The reaction solution is transferred in the sealing reaction kettle of 100ml, and places institute in step (1)
Nickel foam after the small pieces cleaning stated carries out hydro-thermal process using electrical heating, and temperature is 180 DEG C, and time 8h obtains hydro-thermal
Product;
(4) processing step of hydrothermal product:Obtained hydrothermal product is naturally cooled into room temperature, it is clear with water, ethyl alcohol alternating
It washes, amounts to six times, dry 12h, obtains target product, i.e., foamed nickel supported nano bar-shape molybdic acid in 80 DEG C of thermostatic drying chamber
Cobalt.
Structure table is carried out to final foamed nickel supported nano bar-shape cobalt molybdate sample obtained using x-ray powder diffraction instrument
Sign, the results are shown in Figure 1.
Pattern table is carried out to final foamed nickel supported nano bar-shape cobalt molybdate sample obtained using scanning electron microscope
Sign, the results are shown in Figure 2, from (a) in Fig. 2 as can be seen that foam nickel surface covers one layer of cobalt molybdate, and excessive molybdenum
Sour cobalt is rodlike to be attached to cobalt molybdate surface layer;It is uniform that the uniform nano bar-shape cobalt molybdate of pattern is can be seen that from (b) in Fig. 2
It is covered in foam nickel surface.Nanorod diameter is 60-70 nanometers, and length is 200-250 nanometers.
By foamed nickel supported nano bar-shape cobalt molybdate negative material manufactured in the present embodiment and acetylene black and Kynoar
By 7:2:1 mass ratio grinds in N-Methyl pyrrolidone (NMP) medium and slurry is made, and is coated on copper foil, dry, cuts
Piece.It is to electrode with metal lithium sheet, polypropylene screen is diaphragm, 1M LiPF6/ (EC+DMC+EMC) is electrolyte, assembles 2032 types
Number experimental cell carries out electrochemical property test.
As shown in figure 3, in 0.01-3V, with the foamed nickel supported nano bar-shape molybdenum measured under the sweep speed of 0.1mV/s
The CV curve graphs of sour cobalt.The second circle and third circle essentially coincide in addition to first circle, show excellent cycle performance;In cathode for the first time
Under scan pattern, cobalt molybdate is destructurized, and divalent cobalt ion and tetravalence molybdenum lithium ion occur reduction reaction and be reduced to respectively
Metallic cobalt and metal molybdenum, and show unobvious with the alloying of lithium;Under anodic scan pattern, oxygen occurs for metallic cobalt and metal molybdenum
Change reaction and is oxidized to divalent cobalt ion and tetravalence molybdenum ion, sexavalence molybdenum ion respectively.
Fig. 4 and Fig. 5 is respectively the capacitance-voltage curves figure and capacity of prepared foamed nickel supported nano bar-shape cobalt molybdate
(coulombic efficiency)-cyclic curve figure.From Fig. 4,5 as can be seen that in 0.01-3V, with 500mAg-1Current density under, warp
After crossing 100 cycles, capacity stills remain in 760mAhg-1Reversible specific capacity.
As shown in fig. 6, for the capacity versus cycle curve graph measured at 0.01-3V, different current densities.It can from figure
To find out, in 2000mAg-1High current density under, foamed nickel supported nano bar-shape cobalt molybdate shows 480mAhg-1's
Reversible specific capacity, when current density is reduced to 100mAg-1When, reversible specific capacity reaches 1500mAhg again-1, show excellent
Different high rate performance.
Embodiment 2
The present embodiment prepares foamed nickel supported nano bar-shape cobalt molybdate by hydro-thermal method.
Preparation method includes the following steps:
(1) cleaning of nickel foam:It is 250um or so, small pieces (1cm to take aperture2) nickel foam be sequentially placed into 5ml ethyl alcohol,
In 5ml deionized waters, 5ml 1mol/L hydrochloric acid, 5ml acetone, 5ml ethyl alcohol, 5ml deionized waters, the ultrasonic cleaning in each cleaning solution
Time is 10min;
(2) preparation of reaction solution:Bis- molybdic acid hydrate sodium (0.7mmol) of 0.1694g is weighed respectively and 0.2037g six is hydrated
Cobalt nitrate (0.7mmol) is respectively dissolved in 35ml deionized waters, and after stirring and dissolving, sodium molybdate solution is added drop-wise to cobalt nitrate solution
In, it is stirred when being added dropwise, continues 10min, obtain uniformly mixed reaction solution;
(3) hydrothermal treatment step:The reaction solution is transferred in the sealing reaction kettle of 100ml, and places the one of step (1)
Nickel foam after piece cleaning carries out hydro-thermal process using electrical heating, and temperature is 160 DEG C, and time 12h obtains hydrothermal product;
(4) processing step of hydrothermal product:Obtained hydrothermal product is naturally cooled into room temperature, it is clear with water, ethyl alcohol alternating
It washes, amounts to cleaning six times, dry 12h, obtains the foamed nickel supported nano bar-shape of target product-in 80 DEG C of thermostatic drying chamber
Cobalt molybdate.Nanorod diameter is 60-80 nanometers, and length is 200-300 nanometers.
The electrochemical property test of foamed nickel supported nano bar-shape cobalt molybdate manufactured in the present embodiment:It is prepared with the present embodiment
Foamed nickel supported nano bar-shape cobalt molybdate be raw material be assembled into experimental cell, assemble method is same
Embodiment 1, as a result referring to table 1.
Chemical property of 1 embodiment of table, the 2 foamed nickel supported nano bar-shape cobalt molybdate as negative material
As can be known from Table 1, in 0.01-3V, with 500mAg-1Current density under, by 100 cycle after, capacity is still
So it is maintained at 776mAhg-1Reversible specific capacity.
And the capacity versus cycle curve measured at 0.01-3V, different current densities, it can be seen that in 2000mAg-1
High current density under, foamed nickel supported nano bar-shape cobalt molybdate shows 496mAhg-1Reversible specific capacity, when electric current is close
Degree is reduced to 100mAg-1When, reversible specific capacity reaches 1450mAhg again-1, show excellent high rate performance.
Embodiment 3
The present embodiment prepares foamed nickel supported nano bar-shape cobalt molybdate by hydro-thermal method.
Preparation method includes the following steps:
(1) cleaning of nickel foam:It is 250um or so, small pieces (1cm to take aperture2) nickel foam be sequentially placed into 5ml ethyl alcohol,
In 5ml deionized waters, 5ml 1mol/L hydrochloric acid, 5ml acetone, 5ml ethyl alcohol, 5ml deionized waters, the ultrasonic cleaning in each cleaning solution
Time is 10min, ultrasonic power 3KW;
(2) preparation of reaction solution:Bis- molybdic acid hydrate sodium (0.7mmol) of 0.1694g is weighed respectively and 0.2037g six is hydrated
Cobalt nitrate (0.7mmol) is respectively dissolved in 35ml deionized waters, and after stirring and dissolving, sodium molybdate solution is added drop-wise to cobalt nitrate solution
In, it is stirred when being added dropwise, continues 10min, obtain uniformly mixed reaction solution;
(3) hydrothermal treatment step:The reaction solution is transferred in the sealing reaction kettle of 100ml, and places step (1) and obtains
A piece of cleaning after nickel foam, using electrical heating carry out hydro-thermal process, temperature be 180 DEG C, time 12h, obtain hydro-thermal production
Object;
(4) processing step of hydrothermal product:Obtained hydrothermal product is naturally cooled into room temperature, it is clear with water, ethyl alcohol alternating
It washes total six times, dry 12h, obtains the foamed nickel supported nano bar-shape molybdic acid of target product-in 80 DEG C of thermostatic drying chamber
Cobalt.Nanorod diameter is 60-80 nanometers, and length is 200-300 nanometers.
The electrochemical property test of foamed nickel supported nano bar-shape cobalt molybdate manufactured in the present embodiment:It is prepared with the present embodiment
Foamed nickel supported nano bar-shape cobalt molybdate be raw material be assembled into experimental cell, assemble method is same
Embodiment 1, as a result referring to table 2.
Chemical property of 2 embodiment of table, the 3 foamed nickel supported nano bar-shape cobalt molybdate as negative material
As can be known from Table 2, in 0.01-3V, with 500mAg-1Current density under, by 100 cycle after, capacity is still
So it is maintained at 739mAhg-1Reversible specific capacity.
And the capacity versus cycle curve measured at 0.01-3V, different current densities, it can be seen that in 2000mAg-1
High current density under, foamed nickel supported nano bar-shape cobalt molybdate shows 483mAhg-1Reversible specific capacity, when electric current is close
Degree is reduced to 100mAg-1When, reversible specific capacity reaches 1369mAhg again-1, show excellent high rate performance.
Embodiment 4
The present embodiment prepares foamed nickel supported nano bar-shape cobalt molybdate by hydro-thermal method.
Preparation method includes the following steps:
(1) cleaning of nickel foam:It is 250um or so, small pieces (1cm to take aperture2) nickel foam be sequentially placed into 5ml ethyl alcohol,
In 5ml deionized waters, 5ml 1mol/L hydrochloric acid, 5ml acetone, 5ml ethyl alcohol, 5ml deionized waters, the ultrasonic cleaning in each cleaning solution
Time is 10min;
(2) preparation of reaction solution:Bis- molybdic acid hydrate sodium (0.84mmol) of 0.2033g and six water of 0.2037g are weighed respectively
It closes cobalt nitrate (0.7mmol) to be respectively dissolved in 35ml deionized waters, after stirring and dissolving, sodium molybdate solution is added drop-wise to cobalt nitrate solution
In, it is stirred when being added dropwise and continues 10min, obtain uniformly mixed reaction solution;
(3) hydrothermal treatment step:The reaction solution is transferred in the sealing reaction kettle of 100ml, and places step (1) and obtains
A piece of cleaning after nickel foam, using electrical heating carry out hydro-thermal process, temperature be 180 DEG C, time 8h, obtain hydro-thermal production
Object;
(4) processing step of hydrothermal product:Obtained hydrothermal product is naturally cooled into room temperature, it is clear with water, ethyl alcohol alternating
It washes totally six times, dry 12h, obtains the foamed nickel supported nano bar-shape cobalt molybdate of target product-in 80 DEG C of thermostatic drying chamber.
Nanorod diameter is 60-80 nanometers, and length is 200-300 nanometers.
The chemical property performance test of foamed nickel supported nano bar-shape cobalt molybdate manufactured in the present embodiment:With the present embodiment
Prepare foamed nickel supported nano bar-shape cobalt molybdate be raw material be assembled into experimental cell, assemble method with embodiment 1, as a result referring to
Table 3.
Chemical property of 3 embodiment of table, the 4 foamed nickel supported nano bar-shape cobalt molybdate as negative material
From the table it is found that in 0.01-3V, with 500mAg-1Current density under, by 100 cycle after, capacity is still
So it is maintained at 747mAhg-1Reversible specific capacity.
And the capacity versus cycle curve measured at 0.01-3V, different current densities, it can be seen that in 2000mAg-1
High current density under, foamed nickel supported nano bar-shape cobalt molybdate shows 488mAhg-1Reversible specific capacity, when electric current is close
Degree is reduced to 100mAg-1When, reversible specific capacity reaches 1387mAhg again-1, show excellent high rate performance.
Embodiment 5
The present embodiment prepares foamed nickel supported nano bar-shape cobalt molybdate by hydro-thermal method.
Preparation method includes the following steps:
(1) cleaning of nickel foam:It is 250um or so, small pieces (1cm to take aperture2) nickel foam be sequentially placed into 5ml ethyl alcohol,
In 5ml deionized waters, 5ml 1mol/L hydrochloric acid, 5ml acetone, 5ml ethyl alcohol, 5ml deionized waters, the ultrasonic cleaning in each cleaning solution
Time is 10min;
(2) preparation of reaction solution:Bis- molybdic acid hydrate sodium (0.84mmol) of 0.2033g and six water of 0.2037g are weighed respectively
It closes cobalt nitrate (0.7mmol) to be dissolved in 35ml deionized waters, after stirring and dissolving, sodium molybdate solution is added drop-wise to cobalt nitrate solution
In, it is stirred when being added dropwise and continues 10min, obtain uniformly mixed reaction solution;
(3) hydrothermal treatment step:The reaction solution is transferred in the sealing reaction kettle of 100ml, and places step (1) and obtains
A piece of cleaning after nickel foam, using electrical heating carry out hydro-thermal process, temperature be 180 DEG C, time 12h, obtain hydro-thermal production
Object;
(4) processing step of hydrothermal product:Obtained hydrothermal product is naturally cooled into room temperature, it is clear with water, ethyl alcohol alternating
It washes totally six times, dry 12h, obtains the foamed nickel supported nano bar-shape cobalt molybdate of target product-in 80 DEG C of thermostatic drying chamber.
Nanorod diameter is 60-80 nanometers, and length is 200-300 nanometers.
The electrochemical property test of foamed nickel supported nano bar-shape cobalt molybdate manufactured in the present embodiment:It is prepared with the present embodiment
Foamed nickel supported nano bar-shape cobalt molybdate be raw material be assembled into experimental cell, assemble method is same
Embodiment 1, as a result referring to table 4.
Chemical property of 4 embodiment of table, the 5 foamed nickel supported nano bar-shape cobalt molybdate as negative material
From the table it is found that in 0.01-3V, with 500mAg-1Current density under, by 100 cycle after, capacity is still
So it is maintained at 709mAhg-1Reversible specific capacity.
And the capacity versus cycle curve measured at 0.01-3V, different current densities, it can be seen that in 2000mAg-1
High current density under, foamed nickel supported nano bar-shape cobalt molybdate shows 445mAhg-1Reversible specific capacity, when electric current is close
Degree is reduced to 100mAg-1When, reversible specific capacity reaches 1223mAhg again-1, show excellent high rate performance.
Embodiment 6
The present embodiment prepares foamed nickel supported nano bar-shape cobalt molybdate by hydro-thermal method.
Preparation method includes the following steps:
(1) cleaning of nickel foam:It is 250um or so, small pieces (1cm to take aperture2) nickel foam be sequentially placed into 5ml ethyl alcohol,
In 5ml deionized waters, 5ml 1mol/L hydrochloric acid, 5ml acetone, 5ml ethyl alcohol, 5ml deionized waters, the ultrasonic cleaning in each cleaning solution
Time is 10min;
(2) preparation of reaction solution:Bis- molybdic acid hydrate sodium (0.84mmol) of 0.2033g and six water of 0.2037g are weighed respectively
It closes cobalt nitrate (0.7mmol) to be dissolved in 35ml deionized waters, after stirring and dissolving, sodium molybdate solution is added drop-wise to cobalt nitrate solution
In, it is stirred when being added dropwise and continues 10min, obtain uniformly mixed reaction solution;
(3) hydrothermal treatment step:The reaction solution is transferred in the sealing reaction kettle of 100ml, and places step (1) and obtains
A piece of cleaning after nickel foam, using electrical heating carry out hydro-thermal process, temperature be 180 DEG C, time 8h, obtain hydro-thermal production
Object;
(4) processing step of hydrothermal product:Obtained hydrothermal product is naturally cooled into room temperature, it is clear with water, ethyl alcohol alternating
It washes totally six times, dry 12h, obtains the foamed nickel supported nano bar-shape cobalt molybdate of target product-in 120 DEG C of thermostatic drying chamber.
Nanorod diameter is 60-80 nanometers, and length is 200-300 nanometers.
The chemical property performance test of foamed nickel supported nano bar-shape cobalt molybdate manufactured in the present embodiment:With the present embodiment
Prepare foamed nickel supported nano bar-shape cobalt molybdate be raw material be assembled into experimental cell, assemble method with embodiment 1, as a result referring to
Table 5.
Chemical property of 5 embodiment of table, the 6 foamed nickel supported nano bar-shape cobalt molybdate as negative material
From the figure it is found that in 0.01-3V, with 500mAg-1Current density under, by 100 cycle after, capacity is still
So it is maintained at 716mAhg-1Reversible specific capacity.
And the capacity versus cycle curve measured at 0.01-3V, different current densities, it can be seen that in 2000mAg-1
High current density under, foamed nickel supported nano bar-shape cobalt molybdate shows 453mAhg-1Reversible specific capacity, when electric current is close
Degree is reduced to 100mAg-1When, reversible specific capacity reaches 1305mAhg again-1, show excellent high rate performance.
Embodiment 7
The present embodiment prepares foamed nickel supported nano bar-shape cobalt molybdate by hydro-thermal method.
Preparation method includes the following steps:
(1) cleaning of nickel foam:It is 250um or so, small pieces (1cm to take aperture2) nickel foam be sequentially placed into 5ml ethyl alcohol,
In 5ml deionized waters, 5ml 1mol/L hydrochloric acid, 5ml acetone, 5ml ethyl alcohol, 5ml deionized waters, the ultrasonic cleaning in each cleaning solution
Time is 10min;
(2) preparation of reaction solution:Bis- molybdic acid hydrate sodium (1.12mmol) of 0.27104g and six water of 0.2037g are weighed respectively
It closes cobalt nitrate (0.7mmol) to be respectively dissolved in 35ml deionized waters, after stirring and dissolving, sodium molybdate solution is added drop-wise to cobalt nitrate solution
In, it is stirred when being added dropwise and continues 10min, obtain uniformly mixed reaction solution;
(3) hydrothermal treatment step:The reaction solution is transferred in the sealing reaction kettle of 100ml, and places step (1) and obtains
A piece of cleaning after nickel foam, using electrical heating carry out hydro-thermal process, temperature be 160 DEG C, time 12h, obtain hydro-thermal production
Object;
(4) processing step of hydrothermal product:Obtained hydrothermal product is naturally cooled into room temperature, uses water, ethyl alcohol clear successively
It washes three times, dry 12h, obtains the foamed nickel supported nano bar-shape cobalt molybdate of target product-in 80 DEG C of thermostatic drying chamber.It receives
Rice stick is 60-80 nanometers a diameter of, and length is 200-300 nanometers.
The electrochemical property test of foamed nickel supported nano bar-shape cobalt molybdate manufactured in the present embodiment:It is prepared with the present embodiment
Foamed nickel supported nano bar-shape cobalt molybdate be raw material be assembled into experimental cell, assemble method is same
Embodiment 1, as a result referring to table 6.
Chemical property of 6 embodiment of table, the 7 foamed nickel supported nano bar-shape cobalt molybdate as negative material
In 0.01-3V, with 500mAg-1Current density under, by 100 cycle after, capacity stills remain in
702mAh·g-1Reversible specific capacity.
And the capacity versus cycle curve measured at 0.01-3V, different current densities, it can be seen that in 2000mAg-1
High current density under, foamed nickel supported nano bar-shape cobalt molybdate shows 442mAhg-1Reversible specific capacity, when electric current is close
Degree is reduced to 100mAg-1When, reversible specific capacity reaches 1211mAhg again-1, show excellent high rate performance.
Embodiment 8-11
Embodiment 8-11 is in addition to hydro-thermal reaction temperature and time is different from embodiment 1, other preparation technology parameters and reality
It is identical to apply example 1, electrochemical property test method also join by same embodiment, the hydrothermal synthesizing condition and test result of this four embodiments
It is shown in Table 7.
Chemical property of the foamed nickel supported nano bar-shape cobalt molybdates of 7 embodiment 8-11 of table as negative material
Embodiment 12-15
Embodiment 12-15 is in addition to the drying temperature of reaction product and time are different from embodiment 1, other preparation processes ginseng
Number is same as Example 1, electrochemical property test method also same embodiment, the drying temperature of the reaction product of this four embodiments
With time and test result referring to table 8.
Chemical property of the foamed nickel supported nano bar-shape cobalt molybdates of 8 embodiment 12-15 of table as negative material
Embodiment 16
The cleaning way of the embodiment foam-expelling nickel is different from other than embodiment 1, other techniques are same as Example 1, this
The cleaning of the nickel foam of embodiment is as follows:It is 250um or so to take aperture, the nickel foams of small pieces (1cm2) be sequentially placed into 5ml ethyl alcohol,
In 5ml deionized waters, 5ml 1mol/L hydrochloric acid, 5ml deionized waters, the ultrasonic cleaning time in each cleaning solution is 10min.Electricity
Chemical property test method also same embodiment, test result is referring to table 9.
Chemical property of 9 embodiment of table, the 16 foamed nickel supported nano bar-shape cobalt molybdate as negative material
Embodiment 17
The embodiment is removed:Sodium molybdate solution is added drop-wise in cobalt nitrate solution, and stirring duration when being added dropwise is different from
Other than embodiment 1, other techniques are same as Example 1, and the dropwise addition mixing time of the present embodiment is 3min.Electrochemical property test
Method also same embodiment, test result is referring to table 10.
Chemical property of 10 embodiment of table, the 17 foamed nickel supported nano bar-shape cobalt molybdate as negative material
Claims (10)
1. a kind of preparation method of foamed nickel supported nano bar-shape cobalt molybdate, which is characterized in that include the following steps:
The cleaning step of nickel foam;
The preparation process of reaction solution:Molybdate and cobalt salt difference is soluble in water, after stirring and dissolving, it is molten to respectively obtain molybdate
Liquid and cobalt salt solution;Then the molybdate solution is added drop-wise in the cobalt salt solution, it is lasting to stir, it obtains uniformly mixed
Reaction solution;
Hydrothermal treatment step:The reaction solution is transferred in reaction kettle, and places the nickel foam after cleaning, in closed environment
Lower carry out hydro-thermal process, obtains hydrothermal product;
The processing step of hydrothermal product:The hydrothermal product is naturally cooled into room temperature, cleaned, drying process obtains described
Foamed nickel supported nano bar-shape cobalt molybdate.
2. preparation method according to claim 1, which is characterized in that in the cleaning step of the nickel foam, take foam
Nickel, which is sequentially placed into ethyl alcohol, deionized water, hydrochloric acid, acetone, ethyl alcohol, deionized water, to be cleaned by ultrasonic, the nickel foam after being cleaned;
Preferably, a concentration of 0.5-1mol/L of the hydrochloric acid;The time of each ultrasonic cleaning is 10-20min, power 2-
5Kw。
3. preparation method according to claim 1 or 2, which is characterized in that in the preparation process of the reaction solution, institute
It refers to persistently being stirred when molybdate solution is added dropwise to state lasting stirring;Preferably, the time persistently stirred is 8-15min.
4. according to claim 1-3 any one of them preparation methods, which is characterized in that in the preparation process of the reaction solution
In, the molybdate is sodium molybdate or ammonium molybdate;The cobalt salt is cobalt acetate or cobalt nitrate.
5. according to claim 1-4 any one of them preparation methods, which is characterized in that in the preparation process of the reaction solution
In, the molar ratio of molybdenum and cobalt in the cobalt salt is 1-1.6 in the molybdate in the reaction solution:1, preferably 1-1.2:1;
It is highly preferred that in the reaction solution, molybdenum concentration 5-20mmol/L.
6. according to claim 1-5 any one of them preparation methods, which is characterized in that in the hydrothermal treatment step, institute
It is 2 to state the quality of nickel foam and molybdate and the ratio of cobalt salt gross mass:1-10:1.
7. according to claim 1-6 any one of them preparation methods, which is characterized in that in the hydrothermal treatment step, institute
The temperature for stating hydro-thermal process is 140-200 DEG C, soaking time 2-24h;Preferably, the temperature of the hydro-thermal process is 170-
190 DEG C, soaking time 6-10h;It is highly preferred that in the hydrothermal treatment step, the mode of heating of the hydro-thermal process is
Electrical heating or microwave heating.
8. according to claim 1-7 any one of them preparation methods, which is characterized in that in the processing step of the hydrothermal product
In, the temperature of the drying process is 50-150 DEG C, soaking time 6-15h;Preferably, the temperature of the drying process is
70-90 DEG C, soaking time 8-12h;It is highly preferred that in the processing step of the hydrothermal product, the cleaning refer to water,
Ethyl alcohol alternately cleans, and amounts to six times.
9. a kind of foamed nickel supported nano bar-shape cobalt molybdate prepared using any one of claim 1-8 the methods, pattern are equal
One nano bar-shape cobalt molybdate is equably covered in foam nickel surface, is carried on the nano bar-shape cobalt molybdate in the nickel foam
Size is:Nanorod diameter is 60-80 nanometers, and length is 200-300 nanometers.
10. the answering in lithium ion battery as negative material of the foamed nickel supported nano bar-shape cobalt molybdate described in claim 9
With.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711481258.8A CN108314092B (en) | 2017-12-29 | 2017-12-29 | Foam nickel loaded nano rod-shaped cobalt molybdate and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711481258.8A CN108314092B (en) | 2017-12-29 | 2017-12-29 | Foam nickel loaded nano rod-shaped cobalt molybdate and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108314092A true CN108314092A (en) | 2018-07-24 |
CN108314092B CN108314092B (en) | 2020-10-23 |
Family
ID=62892769
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711481258.8A Active CN108314092B (en) | 2017-12-29 | 2017-12-29 | Foam nickel loaded nano rod-shaped cobalt molybdate and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108314092B (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108389733A (en) * | 2018-03-01 | 2018-08-10 | 哈尔滨商业大学 | A kind of preparation method of cobalt molybdate/foam nickel composite film |
CN109647476A (en) * | 2018-11-20 | 2019-04-19 | 天津大学 | A kind of preparation method of metal and the compound HER catalyst of metal oxide |
CN110773210A (en) * | 2019-11-27 | 2020-02-11 | 哈尔滨师范大学 | Self-supporting rod-shaped phosphorus-doped CoMoO 3Oxygen evolution electrocatalyst and preparation method thereof |
CN111020626A (en) * | 2019-12-09 | 2020-04-17 | 北京工业大学 | Preparation method and application of nickel-molybdenum oxide with 3D nanosheet-nanorod mixed structure |
CN112086634A (en) * | 2020-08-14 | 2020-12-15 | 浙江师范大学 | Defective K0.5Mn2O4Nano material, preparation method and zinc ion battery |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103811189A (en) * | 2014-02-12 | 2014-05-21 | 东华大学 | Preparation method of cobalt molybdate and graphene nanocomposite |
CN105448543A (en) * | 2015-12-29 | 2016-03-30 | 东华大学 | Preparation method for CoMoO4 nanostructure supercapacitor electrode material taking foam nickel as substrate |
CN105810450A (en) * | 2016-03-10 | 2016-07-27 | 同济大学 | Method for synthesizing CoMoO4 loaded on foamed nickel electrode material through solvothermal method |
CN106449138A (en) * | 2016-09-14 | 2017-02-22 | 中国计量大学 | Carbon-coated cobalt molybdate network nanosheet array material, preparation method and application |
CN107068420A (en) * | 2017-04-21 | 2017-08-18 | 河南新太行电源股份有限公司 | A kind of preparation method and application of the sour nickel material of core shell structure cobalt molybdate@cobalts |
-
2017
- 2017-12-29 CN CN201711481258.8A patent/CN108314092B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103811189A (en) * | 2014-02-12 | 2014-05-21 | 东华大学 | Preparation method of cobalt molybdate and graphene nanocomposite |
CN105448543A (en) * | 2015-12-29 | 2016-03-30 | 东华大学 | Preparation method for CoMoO4 nanostructure supercapacitor electrode material taking foam nickel as substrate |
CN105810450A (en) * | 2016-03-10 | 2016-07-27 | 同济大学 | Method for synthesizing CoMoO4 loaded on foamed nickel electrode material through solvothermal method |
CN106449138A (en) * | 2016-09-14 | 2017-02-22 | 中国计量大学 | Carbon-coated cobalt molybdate network nanosheet array material, preparation method and application |
CN107068420A (en) * | 2017-04-21 | 2017-08-18 | 河南新太行电源股份有限公司 | A kind of preparation method and application of the sour nickel material of core shell structure cobalt molybdate@cobalts |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108389733A (en) * | 2018-03-01 | 2018-08-10 | 哈尔滨商业大学 | A kind of preparation method of cobalt molybdate/foam nickel composite film |
CN109647476A (en) * | 2018-11-20 | 2019-04-19 | 天津大学 | A kind of preparation method of metal and the compound HER catalyst of metal oxide |
CN110773210A (en) * | 2019-11-27 | 2020-02-11 | 哈尔滨师范大学 | Self-supporting rod-shaped phosphorus-doped CoMoO 3Oxygen evolution electrocatalyst and preparation method thereof |
CN110773210B (en) * | 2019-11-27 | 2022-06-17 | 哈尔滨师范大学 | Self-supporting rod-shaped phosphorus-doped CoMoO3Oxygen evolution electrocatalyst and preparation method thereof |
CN111020626A (en) * | 2019-12-09 | 2020-04-17 | 北京工业大学 | Preparation method and application of nickel-molybdenum oxide with 3D nanosheet-nanorod mixed structure |
CN112086634A (en) * | 2020-08-14 | 2020-12-15 | 浙江师范大学 | Defective K0.5Mn2O4Nano material, preparation method and zinc ion battery |
CN112086634B (en) * | 2020-08-14 | 2021-11-16 | 浙江师范大学 | Defective K0.5Mn2O4Nano material, preparation method and zinc ion battery |
Also Published As
Publication number | Publication date |
---|---|
CN108314092B (en) | 2020-10-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Zheng et al. | In situ formed LiNi0. 8Co0. 15Al0. 05O2@ Li4SiO4 composite cathode material with high rate capability and long cycling stability for lithium-ion batteries | |
JP6493853B2 (en) | Lithium nickel cobalt aluminum oxide composite positive electrode material, method for producing the same, and lithium ion secondary battery | |
CN108314092A (en) | A kind of foamed nickel supported nano bar-shape cobalt molybdate and its preparation method and application | |
CN105355866B (en) | A kind of preparation method of cobaltosic oxide composite graphite alkene three-dimensional aeroge | |
Fan et al. | NiSe 2 nanooctahedra as anodes for high-performance sodium-ion batteries | |
CN110226251A (en) | Nickel hydroxide active material presoma and preparation method thereof, nickel hydroxide active material and lithium secondary battery | |
Sen et al. | Synthesis of molybdenum oxides and their electrochemical properties against Li | |
CN104538604B (en) | Surface modifying method for lithium nickel manganese oxide positive electrode material | |
Wang et al. | Effects of fast lithium-ion conductive coating layer on the nickel rich layered oxide cathode material | |
Wu et al. | Alleviating structural degradation of nickel-rich cathode material by eliminating the surface Fm3¯ m phase | |
CN107792878B (en) | A kind of preparation method of graded structure titanium dioxide (B) and its application in lithium ion battery | |
CN109659540A (en) | A kind of preparation method of porous carbon coating antimony telluride nanometer sheet and its application as metal ion cell negative electrode material | |
CN110752356A (en) | Preparation method of sodium ion battery anode material of double-metal selenide | |
CN112382747B (en) | Carbon layer coated nano mangano-manganic oxide shell-core structure material and preparation method thereof | |
KR101586294B1 (en) | Heterojunction nano material, negative pole piece of lithium ion battery, and lithium ion battery | |
CN107528060A (en) | A kind of nickelic positive electrode of gradient and preparation method thereof and lithium ion battery | |
Leng et al. | Self-templated formation of hierarchical NiCo2O4 yolk-shell microspheres with enhanced electrochemical properties | |
Chen et al. | TiO2/NiO/reduced graphene oxide nanocomposites as anode materials for high-performance lithium ion batteries | |
Zhao et al. | Enhanced electrochemical properties of LiNiO2-based cathode materials by nanoscale manganese carbonate treatment | |
Du et al. | Confined growth of primary grains towards stabilizing integrated structure of Ni-rich materials | |
CN110534718B (en) | Preparation method of transition metal oxide nanosheet array @ carbon paper electrode | |
Qiao et al. | Nanoneedle-assembled hollow α-Fe2O3 microflowers as Li-ion battery anode with high capacity and good temperature tolerance | |
Zhang et al. | KOH-assisted aqueous synthesis of bimetallic metal-organic frameworks and their derived selenide composites for efficient lithium storage | |
Chen et al. | Natural collagen fiber-enabled facile synthesis of carbon@ Fe 3 O 4 core–shell nanofiber bundles and their application as ultrahigh-rate anode materials for Li-ion batteries | |
CN106409520A (en) | Method for preparing electrode material of lithium-ion-mixed capacitor and application thereof |
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 |