CN110416560A - A kind of calcium Mn oxide material and its preparation method and application - Google Patents
A kind of calcium Mn oxide material and its preparation method and application Download PDFInfo
- Publication number
- CN110416560A CN110416560A CN201810388389.XA CN201810388389A CN110416560A CN 110416560 A CN110416560 A CN 110416560A CN 201810388389 A CN201810388389 A CN 201810388389A CN 110416560 A CN110416560 A CN 110416560A
- Authority
- CN
- China
- Prior art keywords
- calcium
- mno
- oxide material
- reaction
- manganese
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of calcium Mn oxide materials and its preparation method and application, by the MnO of synthesis2The calcium nitrate of pipe and different proportion carries out high-temperature calcination after passing through Rotary Evaporators physical mixed again, when calcium ion content is more, MnO2Mn is reduced into after pipe calcining3O4Stick, while being adsorbed on Mn3O4The calcium ion meeting on stick surface and Mn3O4In manganese atom by solid phase reaction converted in-situ be size uniformity calcium manganese oxide particle, due to its valence state is changeable, large specific surface area, heterojunction structure accelerate electron-transport and show excellent oxygen reduction performance.
Description
Technical field
The present invention relates to the preparation methods of converted in-situ calcium Mn oxide, and in particular to calcium ion is in mangano-manganic oxide
(Mn3O4) surface conversion be calcium Mn oxide material preparation method and application.
Background technique
With the in-depth of energy crisis and getting worse for problem of environmental pollution, the development and utilization of new cleaning fuel
It is extremely urgent.In the new cleaning fuel of all polymorphic types, fuel cell directly can convert electric energy for chemical energy because of it
And limited without heat engine process, not by Carnot cycle, energy conversion efficiency is high, the noiseless and advantages such as pollution-free, become most
Has one of the green energy resource of future.
Cathode reaction, that is, redox reactions (oxygen reduction reaction, ORR) of fuel cell are slow because of it
Slow dynamics significantly limits the extensive use of fuel cell, therefore improves catalyst and be always to the catalytic activity of ORR
The research hotspot of fuel cell.Being commercialized most commonly used in fuel cell is the excellent platinum based catalyst of catalytic performance, but by
In the expensive of platinum, scarcity of resources, stability is poor, causes fuel-cell catalyst cost high, substantially increases
The production cost of fuel cell.Therefore, exploitation have high catalytic activity, high stability, low cost nonmetal catalyzed material at
For the significant challenge in the current field.
In recent years, various transition metal oxides were widely studied in terms of electro-catalysis oxygen reduction, wherein manganese base
Oxide is because of cheap, rich reserves and the changeable (Mn of valence state2+、Mn3+、Mn4+、Mn6+And Mn7+), various structures can be formed
Oxide and composite oxides (perovskite, spinels), synthetic method is simple, and show preferable ORR activity and
As research hotspot.Compared to other Mn oxides (such as MnO2、Mn2O3), hausmannite Mn3O4It is most stable of oxidation at high temperature
Object is important industrial chemicals, and its mixed valence (Mn2+、Mn3+、Mn4+) characteristic there is it in some catalytic process
Activity, especially electrocatalysis characteristic during oxygen reduction are always research hotspot.
Recent studies suggest that calcium (Ca) incorporation Mn oxide can largely be improved to their water oxidation activity,
Ca also has important role to the ORR electro-catalysis process of Ca-Mn-O oxide, can influence the absorption of Surface Oxygen, activate and go back
It is former.Meanwhile the combination of calcium ion and manganese improves the chemistry and structural stability of crystal.Reported calcium Mn oxide such as calcium titanium
The CaMnO of mine structure3, layer structure Ca2MnO4、Ca2Mn3O8With the CaMn of rear spinel-type2O4、Ca Mn3O6It is anti-as ORR
The catalyst answered all has preferable activity, but these metal composite oxides all exist that size is larger, specific surface area is lesser
Problem, therefore electrocatalysis characteristic of calcium Mn oxide during oxygen reduction also can further improve.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of calcium Mn oxide materials and preparation method thereof
And application, by the MnO of synthesis2It manages and is forged with the calcium nitrate of different proportion by carrying out high temperature again after Rotary Evaporators physical mixed
It burns, when calcium ion content is more, MnO2Mn is reduced into after pipe calcining3O4Stick, while being adsorbed on Mn3O4The calcium ion on stick surface
Meeting and Mn3O4In manganese atom by solid phase reaction converted in-situ be size uniformity calcium manganese oxide particle, since its valence state is more
Change, large specific surface area, heterojunction structure accelerate electron-transport and show excellent oxygen reduction performance.
The present invention is achieved by the following technical solutions:
A kind of calcium Mn oxide material, including the calcium manganese oxide particle in the distribution of cluster shape, the calcium Mn oxide
The partial size of grain is 20-395nm；It prepares as steps described below:
Step 1, the concentrated hydrochloric acid of 37wt% is slowly added in deionized water, 0.45 gram of potassium permanganate is then added,
The volume ratio of middle concentrated hydrochloric acid and deionized water is 1:40, and ultrasonic agitation half an hour is placed in hydrothermal reaction kettle, at 130-150 DEG C
Under the conditions of react 10-12h, reaction product is successively used to deionized water and ethanol washing 3-5 times after being cooled to room temperature, is placed in vacuum
In drying box, 4-8h is dried at room temperature, obtains brownish black reaction product MnO2Nanotube；
Step 2, MnO step 1 obtained2Nanotube is dissolved in ethanol solution, and calcium nitrate is added, sonicated to make
MnO2Nanotube and calcium nitrate are uniformly distributed with ethanol solution, by Rotary Evaporators solvent evaporated, obtain MnO2With calcium nitrate
Mix products, wherein the molar ratio of manganese and calcium be 1:(1-2)；
Step 3, sample obtained in step 2 is placed in tube furnace, from 20-25 DEG C of room temperature with 1-3 in air atmosphere
DEG C/heating rate of min rises to 800-900 DEG C, with 20-25 DEG C of furnace cooled to room temperature after constant temperature 3-5h, it is adsorbed on Mn3O4
The calcium ion meeting on stick surface and Mn3O4In manganese atom by solid phase reaction converted in-situ be size uniformity calcium Mn oxide
Grain, obtains calcium Mn oxide material.
In the above-mentioned technical solutions, the partial size of the calcium manganese oxide particle is preferably 25-125nm.
In the above-mentioned technical solutions, the reaction temperature being placed in hydrothermal reaction kettle in the step 1 is preferably 135-145
DEG C, the reaction time is preferably 11-12h.
In the above-mentioned technical solutions, in the step 2, the additional amount of calcium nitrate is 0.2-0.6g, preferably 0.25-
0.55g。
In the above-mentioned technical solutions, the heating rate in the step 3 is preferably 1.5-2.5 DEG C/min, and thermostat temperature is excellent
It is selected as 800-850 DEG C, constant temperature time is preferably 3.5-4.5h.
A kind of preparation method of calcium Mn oxide material carries out as steps described below:
Step 1, the concentrated hydrochloric acid of 37wt% is slowly added in deionized water, 0.45 gram of potassium permanganate is then added,
The volume ratio of middle concentrated hydrochloric acid and deionized water is 1:40, and ultrasonic agitation half an hour is placed in hydrothermal reaction kettle, at 130-150 DEG C
Under the conditions of react 10-12h, reaction product is successively used to deionized water and ethanol washing 3-5 times after being cooled to room temperature, is placed in vacuum
In drying box, 4-8h is dried at room temperature, obtains brownish black reaction product MnO2Nanotube；
In step 1, the reaction temperature being placed in hydrothermal reaction kettle is preferably 135-145 DEG C, and the reaction time is preferably 11-
12h；
Step 2, MnO step 1 obtained2Nanotube is dissolved in ethanol solution, and calcium nitrate is added, sonicated to make
MnO2Nanotube and calcium nitrate are uniformly distributed with ethanol solution, by Rotary Evaporators solvent evaporated, obtain MnO2With calcium nitrate
Mix products, wherein the molar ratio of manganese and calcium be 1:(1-2)；
In step 2, the additional amount of calcium nitrate is 0.2-0.6g, preferably 0.25-0.55g；
Step 3, sample obtained in step 2 is placed in tube furnace, from 20-25 DEG C of room temperature with 1-3 in air atmosphere
DEG C/heating rate of min rises to 800-900 DEG C, with 20-25 DEG C of furnace cooled to room temperature after constant temperature 3-5h, it is adsorbed on Mn3O4
The calcium ion meeting on stick surface and Mn3O4In manganese atom by solid phase reaction converted in-situ be size uniformity calcium Mn oxide
Grain, obtains calcium Mn oxide material；
In step 3, heating rate is preferably 1.5-2.5 DEG C/min, and thermostat temperature is preferably 800-850 DEG C, when constant temperature
Between preferably 3.5-4.5h.
A kind of application of calcium Mn oxide material in electro-catalysis oxygen reduction.
The advantages and benefits of the present invention are:
(1) calcium Mn oxide material of the invention prepares the oxygen that calcium Mn oxide optimizes sample using in situ conversion process
Reducing property.
(2) present invention by be modified, make the electro-catalysis oxygen reducing property of sample closer to business platinum carbon, and have at
The feature that this is low, stability is strong.
(3) present invention can apply to the fields such as fuel cell, and are other novel supported heterojunction structure elctro-catalysts
Design opens new approaches with synthesis.
Detailed description of the invention
Fig. 1 is the electron scanning micrograph of calcium Mn oxide material prepared by the embodiment of the present invention one.
Fig. 2 is the electron scanning micrograph of calcium Mn oxide material prepared by the embodiment of the present invention two.
Fig. 3 is the XRD diagram of calcium Mn oxide material prepared by the embodiment of the present invention one.
Fig. 4 is the XRD diagram of calcium Mn oxide material prepared by the embodiment of the present invention two.
Fig. 5 is calcium Mn oxide material prepared by the embodiment of the present invention one and calcium Mn oxide material prepared by embodiment two
The performance comparison figure of material.
Specific embodiment
In order to enable those skilled in the art to better understand the solution of the present invention, with reference to the accompanying drawing with specific embodiment into
One step illustrates technical solution of the present invention.It should be understood that following embodiments be it is illustrative, be not restrictive, cannot
It is limited the scope of protection of the present invention with following embodiments.Required raw material is the commercially available pure examination of chemistry in following embodiment
Agent.
Embodiment one
Raw material: concentrated hydrochloric acid solution, potassium permanganate, calcium nitrate.
(1) during stirring, the concentrated hydrochloric acid of 1 milliliter of 37wt% is slowly added in 40 milliliters of deionized water,
Then 0.45 gram of potassium permanganate is added, stirring half an hour keeps the hydro-thermal for pouring into 50 milliliters after its is evenly dispersed anti-with ultrasonic machine again
It answers in kettle, is placed in 140 degree of baking oven and reacts 12 hours.Kettle to be reflected is cooled to room temperature, by brownish black reaction product MnO2It receives
Mitron deionized water and ethyl alcohol wash 3 times repeatedly, then drying at room temperature 6 hours in a vacuum drying oven, and it is anti-to obtain brownish black
Answer product MnO2Nanotube；
(2) by 0.1 gram of MnO2Nanotube is dissolved in 10 milliliters of ethyl alcohol, and 0.27 gram of calcium nitrate is added so that manganese with
The molar ratio of calcium is 1:1, sonicated that the two is made uniformly to mix dispersion in a solvent, by Rotary Evaporators solvent is steamed
It is dry, obtain the mix products of manganese dioxide and calcium nitrate；
(3) the resulting sample of previous step is placed in tube furnace, is risen in air atmosphere with the heating rate of 2 DEG C/min
850 degree, constant temperature 4 hours, obtain final product CaMnO3。
Embodiment two
Raw material: concentrated hydrochloric acid solution, potassium permanganate, calcium nitrate.
(1) during stirring, the concentrated hydrochloric acid of 1 milliliter of 37wt% is slowly added in 40 milliliters of deionized water,
Then 0.45 gram of potassium permanganate is added, stirring half an hour keeps the hydro-thermal for pouring into 50 milliliters after its is evenly dispersed anti-with ultrasonic machine again
It answers in kettle, is placed in 140 degree of baking oven and reacts 12 hours.Kettle to be reflected is cooled to room temperature, by brownish black reaction product MnO2It receives
Mitron deionized water and ethyl alcohol wash 3 times repeatedly, then drying at room temperature 6 hours in a vacuum drying oven, and it is anti-to obtain brownish black
Answer product MnO2Nanotube；
(2) by 0.1 gram of MnO2Nanotube is dissolved in 10 milliliters of ethyl alcohol, and 0.54 gram of calcium nitrate is added so that manganese with
The molar ratio of calcium is 1:2, sonicated that the two is made uniformly to mix dispersion in a solvent, by Rotary Evaporators solvent is steamed
It is dry, obtain the mix products of manganese dioxide and calcium nitrate；
(3) the resulting sample of previous step is placed in tube furnace, is risen in air atmosphere with the heating rate of 2 DEG C/min
850 degree, constant temperature 4 hours, obtain final product Ca2MnO4。
By Fig. 1 calcium Mn oxide material (CaMnO3) electron scanning micrograph and Fig. 2 calcium Mn oxide material
(Ca2MnO4) electron scanning micrograph can be seen that increasing with calcium ion content, obtained calcium manganese oxide particle
Size gradually fine uniform.
It can be seen from Fig. 3 and Fig. 4 when the molar ratio of manganese and calcium is 1:1, obtained calcium Mn oxide material is
CaMnO3；When the molar ratio of manganese and calcium is 1:2, obtained calcium Mn oxide material is Ca2MnO4。
By Fig. 5 calcium Mn oxide material CaMnO3With Ca2MnO4Performance comparison figure can be seen that perovskite structure
CaMnO3Than the Ca of Ruddlesden-Popper structure2MnO4Performance is more excellent.
Test uses three-electrode system, and used test equipment is Shanghai Chen Hua electrochemical workstation and U.S. Pine rotation
Turn disk electrode, working electrode is respectively CaMnO3With Ca2MnO4, it is platinum column to electrode, reference electrode is mercury/mercuric oxide electrode,
Electrolyte is the KOH solution that concentration is 0.1M.
Although above example combination attached drawing compares detailed description to the invention, the invention is not limited to
The preparation of calcium Mn oxide material can be achieved according to the adjustment that summary of the invention carries out technological parameter for the specific embodiment stated,
And show the performance almost the same with above-described embodiment.It should be noted that in the case where not departing from core of the invention,
Any simple deformation, modification or the various forms of transformation that creative work can not be spent to make under present invention enlightenment
Each fall within protection scope of the present invention.
Claims (10)
1. a kind of calcium Mn oxide material, including the calcium manganese oxide particle in the distribution of cluster shape, the calcium manganese oxide particle
Partial size be 20-395nm；It prepares as steps described below:
Step 1, the concentrated hydrochloric acid of 37wt% is slowly added in deionized water, 0.45 gram of potassium permanganate is then added, wherein dense
The volume ratio of hydrochloric acid and deionized water is 1:40, and ultrasonic agitation half an hour is placed in hydrothermal reaction kettle, in 130-150 DEG C of condition
Reaction product is successively used deionized water and ethanol washing 3-5 times, is placed in vacuum drying by lower reaction 10-12h after being cooled to room temperature
In case, 4-8h is dried at room temperature, obtains brownish black reaction product MnO2Nanotube；
Step 2, MnO step 1 obtained2Nanotube is dissolved in ethanol solution, and calcium nitrate is added, sonicated to make MnO2It receives
Mitron and calcium nitrate are uniformly distributed with ethanol solution, by Rotary Evaporators solvent evaporated, obtain MnO2With mixing for calcium nitrate
Product is closed, wherein the molar ratio of manganese and calcium is 1:(1-2)；
Step 3, sample obtained in step 2 is placed in tube furnace, in air atmosphere from 20-25 DEG C of room temperature with 1-3 DEG C/
The heating rate of min rises to 800-900 DEG C, with 20-25 DEG C of furnace cooled to room temperature after constant temperature 3-5h, is adsorbed on Mn3O4Stick table
The calcium ion meeting in face and Mn3O4In manganese atom by solid phase reaction converted in-situ be size uniformity calcium manganese oxide particle, obtain
To calcium Mn oxide material.
2. a kind of calcium Mn oxide material according to claim 1, it is characterised in that: the grain of the calcium manganese oxide particle
Diameter is preferably 25-125nm.
3. a kind of calcium Mn oxide material according to claim 1 or 2, it is characterised in that: be placed in hydro-thermal in the step 1
Reaction temperature in reaction kettle is preferably 135-145 DEG C, and the reaction time is preferably 11-12h.
4. a kind of calcium Mn oxide material according to claim 1, it is characterised in that: in the step 2, calcium nitrate adds
Entering amount is 0.2-0.6g, preferably 0.25-0.55g.
5. a kind of calcium Mn oxide material according to claim 1, it is characterised in that: the heating rate in the step 3
Preferably 1.5-2.5 DEG C/min, thermostat temperature is preferably 800-850 DEG C, and constant temperature time is preferably 3.5-4.5h.
6. a kind of preparation method of calcium Mn oxide material, it is characterised in that: carry out as steps described below:
Step 1, the concentrated hydrochloric acid of 37wt% is slowly added in deionized water, 0.45 gram of potassium permanganate is then added, wherein dense
The volume ratio of hydrochloric acid and deionized water is 1:40, and ultrasonic agitation half an hour is placed in hydrothermal reaction kettle, in 130-150 DEG C of condition
Reaction product is successively used deionized water and ethanol washing 3-5 times, is placed in vacuum drying by lower reaction 10-12h after being cooled to room temperature
In case, 4-8h is dried at room temperature, obtains brownish black reaction product MnO2Nanotube；
Step 2, MnO step 1 obtained2Nanotube is dissolved in ethanol solution, and calcium nitrate is added, sonicated to make MnO2It receives
Mitron and calcium nitrate are uniformly distributed with ethanol solution, by Rotary Evaporators solvent evaporated, obtain MnO2With mixing for calcium nitrate
Product is closed, wherein the molar ratio of manganese and calcium is 1:(1-2)；
Step 3, sample obtained in step 2 is placed in tube furnace, in air atmosphere from 20-25 DEG C of room temperature with 1-3 DEG C/
The heating rate of min rises to 800-900 DEG C, with 20-25 DEG C of furnace cooled to room temperature after constant temperature 3-5h, is adsorbed on Mn3O4Stick table
The calcium ion meeting in face and Mn3O4In manganese atom by solid phase reaction converted in-situ be size uniformity calcium manganese oxide particle, obtain
To calcium Mn oxide material.
7. preparation method according to claim 6, it is characterised in that: in step 1, the reaction being placed in hydrothermal reaction kettle
Temperature is preferably 135-145 DEG C, and the reaction time is preferably 11-12h.
8. preparation method according to claim 6, it is characterised in that: in step 2, the additional amount of calcium nitrate is 0.2-
0.6g, preferably 0.25-0.55g.
9. preparation method according to claim 6, it is characterised in that: in step 3, heating rate is preferably 1.5-2.5
DEG C/min, thermostat temperature is preferably 800-850 DEG C, and constant temperature time is preferably 3.5-4.5h.
10. a kind of application of calcium Mn oxide material as described in claim 1 in electro-catalysis oxygen reduction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810388389.XA CN110416560B (en) | 2018-04-26 | 2018-04-26 | Calcium manganese oxide material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810388389.XA CN110416560B (en) | 2018-04-26 | 2018-04-26 | Calcium manganese oxide material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110416560A true CN110416560A (en) | 2019-11-05 |
| CN110416560B CN110416560B (en) | 2022-05-20 |
Family
ID=68346062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810388389.XA Active CN110416560B (en) | 2018-04-26 | 2018-04-26 | Calcium manganese oxide material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110416560B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111320211A (en) * | 2020-03-02 | 2020-06-23 | 吉林师范大学 | Perovskite type calcium manganate material, preparation method thereof and application thereof in wide-temperature-zone lithium ion battery |
| CN111871422A (en) * | 2020-07-21 | 2020-11-03 | 上海交通大学 | Application of calcium-manganese oxide catalyst in degradation of organic pollutants in wastewater and soil |
| CN112156766A (en) * | 2020-09-25 | 2021-01-01 | 天津大学 | Two-dimensional layered metal calcium/indium double hydroxide and preparation method and application thereof |
| CN114656243A (en) * | 2022-02-25 | 2022-06-24 | 纯钧新材料(深圳)有限公司 | Calcium-manganese-oxygen thermoelectric material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11317225A (en) * | 1998-04-30 | 1999-11-16 | Mitsubishi Materials Corp | Positive active material for lithium secondary battery and its manufacture |
| US20100327238A1 (en) * | 2008-02-14 | 2010-12-30 | Sumitomo Chemical Company, Limited | Sintered body and thermoelectric material |
| JP2012028504A (en) * | 2010-07-22 | 2012-02-09 | Jgc Catalysts & Chemicals Ltd | CaMnO3 TYPE THERMOELECTRIC CONVERSION MATERIAL AND METHOD FOR PRODUCING THE SAME |
| CN102867965A (en) * | 2012-09-29 | 2013-01-09 | 南开大学 | Porous microsphere perovskite type calcium manganese oxide compound and preparation method and application thereof |
| CN105280393A (en) * | 2015-11-24 | 2016-01-27 | 华南师范大学 | Amorphous carbon material for nano tunnel and preparation method thereof |
| CN107507908A (en) * | 2017-08-30 | 2017-12-22 | 贵州大学 | A kind of solid phase method prepares low-resistivity CaxR1‑xMnO3‑Bi2O3The method of composite thermoelectric material |
-
2018
- 2018-04-26 CN CN201810388389.XA patent/CN110416560B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11317225A (en) * | 1998-04-30 | 1999-11-16 | Mitsubishi Materials Corp | Positive active material for lithium secondary battery and its manufacture |
| US20100327238A1 (en) * | 2008-02-14 | 2010-12-30 | Sumitomo Chemical Company, Limited | Sintered body and thermoelectric material |
| JP2012028504A (en) * | 2010-07-22 | 2012-02-09 | Jgc Catalysts & Chemicals Ltd | CaMnO3 TYPE THERMOELECTRIC CONVERSION MATERIAL AND METHOD FOR PRODUCING THE SAME |
| CN102867965A (en) * | 2012-09-29 | 2013-01-09 | 南开大学 | Porous microsphere perovskite type calcium manganese oxide compound and preparation method and application thereof |
| CN105280393A (en) * | 2015-11-24 | 2016-01-27 | 华南师范大学 | Amorphous carbon material for nano tunnel and preparation method thereof |
| CN107507908A (en) * | 2017-08-30 | 2017-12-22 | 贵州大学 | A kind of solid phase method prepares low-resistivity CaxR1‑xMnO3‑Bi2O3The method of composite thermoelectric material |
Non-Patent Citations (3)
| Title |
|---|
| WEI XIAO, ET AL.: "Growth of single-crystal α-MnO2 nanotubes prepared by a hydrothermal route and their electrochemical properties", 《JOURNAL OF POWER SOURCES》 * |
| 王琴等: "CaMnO3热电材料的低温烧结研究", 《西华大学学报(自然科学版)》 * |
| 韩晓鹏: "CaMnO3基微纳材料制备及电催化性能研究", 《万方平台博士论文数据库》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111320211A (en) * | 2020-03-02 | 2020-06-23 | 吉林师范大学 | Perovskite type calcium manganate material, preparation method thereof and application thereof in wide-temperature-zone lithium ion battery |
| CN111871422A (en) * | 2020-07-21 | 2020-11-03 | 上海交通大学 | Application of calcium-manganese oxide catalyst in degradation of organic pollutants in wastewater and soil |
| CN112156766A (en) * | 2020-09-25 | 2021-01-01 | 天津大学 | Two-dimensional layered metal calcium/indium double hydroxide and preparation method and application thereof |
| CN112156766B (en) * | 2020-09-25 | 2022-08-19 | 天津大学 | Two-dimensional layered metal calcium/indium double hydroxide and preparation method and application thereof |
| CN114656243A (en) * | 2022-02-25 | 2022-06-24 | 纯钧新材料(深圳)有限公司 | Calcium-manganese-oxygen thermoelectric material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110416560B (en) | 2022-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106955691B (en) | A kind of monatomic iron catalyst of carbon-to-nitrogen base and preparation method thereof | |
| CN109065897B (en) | Phosphorus-doped porous carbon-coated cobaltosic oxide oxygen reduction catalyst and preparation method and application thereof | |
| CN110416560A (en) | A kind of calcium Mn oxide material and its preparation method and application | |
| CN107694581B (en) | Application of heteroatom-doped porous carbon-coated cuprous phosphide composite catalyst | |
| CN109174157B (en) | Preparation method of cobalt-nitrogen co-doped biomass carbon oxidation reduction catalyst | |
| CN109728311B (en) | Metal organic framework compound hollow microsphere loaded with iron cobalt sulfide | |
| CN109659570B (en) | Application of metal organic framework compound hollow microspheres loaded with iron cobalt sulfide | |
| CN114293223B (en) | Method for preparing superfine cerium dioxide supported metal monoatomic catalyst from cluster-based framework material | |
| CN110611105B (en) | Preparation method of ORR catalyst | |
| CN104157858B (en) | Classifying porous ferroso-ferric oxide/graphene nano line and its preparation method and application | |
| CN111634954B (en) | Iron-modified cobalt-iron oxide with self-assembled flower ball structure and preparation and application thereof | |
| CN112221530A (en) | Preparation method and application of non-noble metal single-atom dual-function electrocatalyst | |
| CN114772653B (en) | Preparation and application of hollow cobaltosic oxide carbon-nitrogen composite material | |
| CN110048134A (en) | A kind of universality method preparing porous nitrogen fluorine codope carbon oxygen reduction catalyst | |
| CN110721713A (en) | Mo2C catalytic material and preparation method and application thereof | |
| CN110961162A (en) | Catalyst carrier, precious metal catalyst, and preparation method and application thereof | |
| CN113067000A (en) | Oxygen vacancy-containing TiO2Upper load Pd-Co nano alloy catalyst and preparation method and application thereof | |
| CN110492112A (en) | A kind of hydrogen reduction composite catalyst and preparation method thereof | |
| CN110655120B (en) | Preparation method of mesoporous spherical nickel cobaltate nano material | |
| CN113611881A (en) | Atomic-level dispersed Fe/nitrogen-doped mesoporous carbon spheres and preparation method and application thereof | |
| CN114477163B (en) | Iron/nitrogen co-doped single-atom carbon catalyst and preparation method thereof | |
| CN109731599B (en) | 2D oxygen reduction catalyst Fe3O4Preparation method of @ FeNC nanosheet | |
| CN113549937A (en) | For CO2Electrocatalytic material Cu of RR2Preparation method of O @ h-BN | |
| CN110400937B (en) | Preparation method and application of manganese cobalt oxide with porous spherical hollow structure | |
| CN103240080A (en) | Application of manganese oxide/graphene catalyst |
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 |