CN104779386B - Manganese cobaltate octahedral nanomaterial and preparation method thereof - Google Patents
Manganese cobaltate octahedral nanomaterial and preparation method thereof Download PDFInfo
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- CN104779386B CN104779386B CN201510132991.3A CN201510132991A CN104779386B CN 104779386 B CN104779386 B CN 104779386B CN 201510132991 A CN201510132991 A CN 201510132991A CN 104779386 B CN104779386 B CN 104779386B
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- octahedral
- nanomaterial
- manganese cobaltate
- deionized water
- cobalt acid
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- 239000011572 manganese Substances 0.000 title claims abstract description 44
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 39
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000002086 nanomaterial Substances 0.000 title abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 20
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 33
- 239000010941 cobalt Substances 0.000 claims description 30
- 229910017052 cobalt Inorganic materials 0.000 claims description 30
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 26
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 4
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 4
- 239000002244 precipitate Substances 0.000 abstract 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910003168 MnCo2O4 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- -1 octyl phenyl Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a manganese cobaltate octahedral nanomaterial and a preparation method thereof. The method comprises the following steps: dissolving Mn(NO3)2 and Co(NO3)2.6H2O in deionized water, and adding anhydrous ethanol; adding polyethylene glycol octylphenol ether to the above obtained solution according to a molar ratio of nitrate to polyethylene glycol octylphenol ether of 1:4-1:0.25, transferring the obtained solution to a hydrothermal reaction kettle, and reacting; and opening the kettle, centrifuging, separating the obtained precipitate, washing the precipitate with deionized water and alcohol, and drying at 60-80DEG C to obtain the manganese cobaltate octahedral nanomaterial. The particle dimension of the manganese cobaltate octahedral nanomaterial prepared in the invention is not greater than 400nm. The manganese cobaltate octahedral nanomaterial can be used as a lithium ion battery. Test results show that the first discharge capacity of the manganese cobaltate octahedral nanomaterial under a current density of 50-200mAg＜-1＞ reaches 1400mAhg＜-1＞, and the specific capacity of the manganese cobaltate octahedral nanomaterial after 25 cycles still reaches above 750mAhg＜-1＞; and the preparation method has the characteristics of simple operation and energy saving.
Description
Technical field
The invention belongs to inorganic nano material synthesis field.In particular, it is related to be prepared with surfactant hydro-thermal method
Cobalt acid manganese nanometer octahedron material and method.
Background technology
Cobalt acid manganese (MnCo2O4.5) material is the negative material being applied to lithium ion battery, MnCo2O4.5Than common
MnCo2O4Many 0.5 O atom, that is, produce many rooms, good conductivity, overcome other transition metal oxide poorly conductives
Shortcoming.MnCo2O4.5For the composite oxides of manganese and cobalt, both maintain the cyclical stability of Mn oxide, have cobalt/cobalt oxide again concurrently
Height ratio capacity characteristic.Using MnCo2O4.5As lithium ion battery negative material, not only raw material rich reserves, cheap,
And specific capacity is high.MnCo2O4.5Lithium is stored up by redox reaction, metal oxide is reduced into metal crystalline substance when lithium embeds
Body (Mn and Co) is dispersed in lithia matrix, and when lithium is deviate from, they are oxidized to corresponding metal oxide again, thus cobalt
The reversible theoretical capacity of manganese composite oxide is apparently higher than graphite.
Although the composite oxide cathode material of the different-shape being obtained at present has very high capacity, its capacity attenuation
Too fast, become the matter of utmost importance limiting its practical application.The oxide cathode material of nanosizing passes through to increase electrolyte and activity
The contact area of material is so that the internal resistance of battery reduces, and during charge and discharge cycles, can reduce lithium ion and electronics
Diffusion transport distance, thus to a certain extent improve material performance of lithium ion battery.So, how to prepare particle size
Little and homogeneous nanometer cobalt manganese composite oxide, is to prepare efficient cobalt urgently to be resolved hurrily the asking of manganese composite oxide lithium cell negative pole material
Topic.
Content of the invention
The purpose of the present invention is by Value 3608 surfactant hydro-thermal method, makes crystal grain in growth
Obtain effective appearance and size to control, there is provided a kind of method preparing single-size cobalt acid manganese nanometer octahedron material.
The invention provides a kind of method preparing single-size cobalt acid manganese nanometer octahedron material, the method is in hydro-thermal
On the basis of, using Value 3608 as surfactant, a step obtains the homogeneous cobalt acid manganese of appearance and size and receives
The octahedra material of rice.Cobalt acid manganese nanometer octahedron material particles size is little, and specific surface area is big, can reduce the internal resistance of cell, reduces lithium
The diffusion transport distance of ion and electronics, is conducive to improving the performance of lithium ion battery.In 50-200mAg-1Current density under
Test its performance, discharge capacity is up to 1400mAhg first-1More than, circulation 25 times afterwards its specific capacity still up to 750mAhg-1
More than.
The concrete technical scheme of the present invention is as follows：
The present invention prepares cobalt acid manganese nanometer octahedron material and method, on the basis of hydro-thermal, pungent using polyethyleneglycol
As surfactant, a step obtains cobalt acid manganese nanometer octahedron material to base phenyl ether.
Comprise the following steps that:
1). by Mn (NO3)2、Co(NO3)2·6H2O is dissolved in deionized water, adds absolute ethyl alcohol, deionized water and anhydrous
The volume ratio of ethanol is 1:2-1:0.5；
2). to step 1) add Value 3608, nitrate and polyethyleneglycol octyl phenyl in solution
The mol ratio of ether is 1:4～1:0.25, it is then transferred into reaction in hydrothermal reaction kettle；
3). open centrifugation sediment, deionized water and ethanol wash after kettle, be then dried to obtain at 60-80 DEG C
Cobalt acid manganese octahedron material.
Described step 1) in, Mn (NO3)2With Co (NO3)2·6H2The mol ratio of O is 1:2.
Described step 2) at a temperature of 120-180 DEG C, heating response 8-12h in hydrothermal reaction kettle.
Prepare cobalt acid manganese nanometer octahedron material particles to be smaller in size than equal to 400nm.Cobalt acid manganese nanometer octahedron material is used
Make lithium ion battery.
The invention provides a kind of surfactant water thermal control preparing single-size cobalt acid manganese nanometer octahedron material
Pattern synthetic method.Other preparation methods relatively, material has nanometer octahedral structure and size uniformity, less than or equal to 400nm,
Equipment is simple, simple process.
The effect of the present invention is：Can one step hydro-thermal prepare single-size cobalt acid manganese nanometer octahedron material, by surface
The addition of activating agent Value 3608, significantly improves the size of cobalt acid manganese material, the pattern of hydro-thermal method preparation
Structure.Cobalt acid manganese nanometer octahedron material particles are smaller in size than equal to 400nm, and specific surface area is big, by increasing capacitance it is possible to increase electrolyte and work
Property material contact area so that the internal resistance of battery reduces, and during charge and discharge cycles, lithium ion and electricity can be reduced
The diffusion transport distance of son, thus improve the performance of lithium ion battery of material to a certain extent.In 50-200mAg-1Electric current
Its performance is tested, discharge capacity is up to 1400mAhg first under density-1More than, circulation 25 times afterwards its specific capacity still up to
750mAhg-1More than.The inventive method has the features such as simple to operate, save energy, raw material are easy to get.
Brief description
Fig. 1 is MnCo prepared by embodiment 12O4.5Stereoscan photograph, illustrate that prepared product has a nanometer octahedral
Body structure, size uniformity and be less than or equal to 400nm.
Fig. 2 is MnCo prepared by embodiment 22O4.5X-ray diffractogram, illustrate that prepared product has pure composition.
Fig. 3 is MnCo prepared by embodiment 32O4.5Stereoscan photograph, illustrate that prepared product has a nanometer octahedral
Body structure, size uniformity and be less than or equal to 400nm.
Specific embodiment
Preferred embodiment method comprises the following steps that：
1). by Mn (NO3)2, Co (NO3)2·6H2O is dissolved in deionized water it is ensured that Mn (NO3)2With Co (NO3)2·6H2O
Mol ratio be 1:2, add absolute ethyl alcohol, the volume ratio of deionized water and absolute ethyl alcohol is 1:2-1:0.5, mix.
2). add Value 3608 in solution, nitrate is rubbed with Value 3608
That ratio is 1:4-1:0.25, transfer to afterwards in hydrothermal reaction kettle, heat 8-12h at a temperature of 120-180 DEG C.
3). open centrifugation sediment after kettle, deionized water and ethanol wash for several times, are then dried at 60-80 DEG C
Can obtain being smaller in size than the cobalt acid manganese octahedron material equal to 400nm.
Embodiment 1：
By 0.002molMn (NO3)2, 0.004Co (NO3)2·6H2O is dissolved in 12ml deionized water, adds the anhydrous second of 24ml
Alcohol, mixes.Add the Value 3608 of 0.024mol, mix, transfer the solution into hydro-thermal reaction
In kettle, heat 12h at a temperature of 120 DEG C.Open centrifugation sediment after kettle, deionized water and ethanol wash for several times, then
It is dried to obtain cobalt acid manganese nanometer octahedron material at 60 DEG C.The stereoscan photograph of prepared cobalt acid manganese is as shown in figure 1, say
Bright prepared product has a nanometer octahedral structure, size uniformity and be less than or equal to 400nm.In 200mAg-1Current density
Lower its performance of test, discharge capacity is up to 1400mAhg first-1More than, circulation 25 times afterwards its specific capacity still up to 750mAhg-1More than.
Embodiment 2：
By 0.002molMn (NO3)2, 0.004Co (NO3)2·6H2O is dissolved in 18ml deionized water, adds the anhydrous second of 18ml
Alcohol, mixes.Add the Value 3608 of 0.006mol, mix, transfer the solution into hydro-thermal reaction
In kettle, heat 10h at a temperature of 150 DEG C.Open centrifugation sediment after kettle, deionized water and ethanol wash for several times, then
It is dried to obtain cobalt acid manganese nanometer octahedron material at 70 DEG C.The X-ray diffraction of prepared cobalt acid manganese nanometer octahedron material
Figure is as shown in Fig. 2 the prepared product of explanation has pure composition.In 100mAg-1Current density under test its performance, first
Discharge capacity is up to 1400mAhg-1More than, circulation 25 times afterwards its specific capacity still up to 750mAhg-1More than.
Embodiment 3：
By 0.002molMn (NO3)2, 0.004Co (NO3)2·6H2O is dissolved in 24ml deionized water, adds the anhydrous second of 12ml
Alcohol, mixes.Add the Value 3608 of 0.0015mol, mix, transfer the solution into hydro-thermal reaction
In kettle, heat 8h at a temperature of 180 DEG C.Open centrifugation sediment after kettle, deionized water and ethanol wash for several times, Ran Hou
It is dried to obtain cobalt acid manganese nanometer octahedron material at 80 DEG C.The stereoscan photograph of prepared cobalt acid manganese material as shown in figure 3,
Illustrate that prepared product has a nanometer octahedral structure, size uniformity and be less than or equal to 400nm.In 50mAg-1Current density
Lower its performance of test, discharge capacity is up to 1400mAhg first-1More than, circulation 25 times afterwards its specific capacity still up to 750mAhg-1More than.
To sum up the accompanying drawing of embodiment can also clearly be found out, the product prepared by the present invention has a nanometer octahedral structure,
Size uniformity and be less than or equal to 400nm.
Claims (3)
1. the method preparing cobalt acid manganese nanometer octahedron material, is characterized in that step is as follows:
1). by Mn (NO3)2、Co(NO3)2·6H2O is dissolved in deionized water, adds absolute ethyl alcohol, deionized water and absolute ethyl alcohol
Volume ratio be 1:2-1:0.5；
2). to step 1) add Value 3608, nitrate and Value 3608 in solution
Mol ratio is 1:4～1:0.25, it is then transferred into reaction in hydrothermal reaction kettle；At a temperature of 120-180 DEG C, in hydrothermal reaction kettle
Middle heating response 8-12h；
3). open centrifugation sediment, deionized water and ethanol wash after kettle, at 60-80 DEG C, be then dried to obtain cobalt acid
Manganese octahedron material.
2. the method for claim 1, is characterized in that described step 1) in, Mn (NO3)2With Co (NO3)2·6H2O rubs
That ratio is 1:2.
3. the method for claim 1, is characterized in that preparing cobalt acid manganese nanometer octahedron material particles and is smaller in size than and be equal to
400nm.
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| CN201510132991.3A CN104779386B (en) | 2015-03-25 | 2015-03-25 | Manganese cobaltate octahedral nanomaterial and preparation method thereof |
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| CN201510132991.3A CN104779386B (en) | 2015-03-25 | 2015-03-25 | Manganese cobaltate octahedral nanomaterial and preparation method thereof |
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| CN104779386B true CN104779386B (en) | 2017-02-22 |
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| CN106115798B (en) * | 2016-06-16 | 2017-10-31 | 齐鲁工业大学 | A kind of MnCo2O4Hexagonal nanometer rods and method for preparing Nano cube |
| CN108598426A (en) * | 2018-04-26 | 2018-09-28 | 吉林大学 | The method for improving its charge/discharge capacity by preparing cobalt acid manganese/N doping carbon/manganese dioxide nucleocapsid |
| CN109119251B (en) * | 2018-08-30 | 2020-04-24 | 中北大学 | Porous MnCo2O4．5Preparation method of electrode material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102468478A (en) * | 2010-11-17 | 2012-05-23 | 中国科学院大连化学物理研究所 | Preparation method of nano-scale compound metal oxide octahedron |
| CN103073072A (en) * | 2013-01-29 | 2013-05-01 | 安泰科技股份有限公司 | Manganese cobalt composite oxide (MnCo2O4) magnetic nanocrystal and preparation method thereof |
| CN103474254A (en) * | 2013-09-26 | 2013-12-25 | 哈尔滨工程大学 | Preparation method for supercapacitor electrode material containing MnCo2O4.5 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102468478A (en) * | 2010-11-17 | 2012-05-23 | 中国科学院大连化学物理研究所 | Preparation method of nano-scale compound metal oxide octahedron |
| CN103073072A (en) * | 2013-01-29 | 2013-05-01 | 安泰科技股份有限公司 | Manganese cobalt composite oxide (MnCo2O4) magnetic nanocrystal and preparation method thereof |
| CN103474254A (en) * | 2013-09-26 | 2013-12-25 | 哈尔滨工程大学 | Preparation method for supercapacitor electrode material containing MnCo2O4.5 |
Non-Patent Citations (1)
| Title |
|---|
| Facile hydrothermal synthesis of urchin-like NiCo2O4 spheres as efficient electrocatalysts for oxygen reduction reaction;Zhao-Qing Liu et al;《Hydrogen Energy》;20130418;第38卷;第6658页左栏第3段 * |
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