CN104733726B - Prepare cobalt acid manganese hollow microspheres and method - Google Patents
Prepare cobalt acid manganese hollow microspheres and method Download PDFInfo
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- CN104733726B CN104733726B CN201510132944.9A CN201510132944A CN104733726B CN 104733726 B CN104733726 B CN 104733726B CN 201510132944 A CN201510132944 A CN 201510132944A CN 104733726 B CN104733726 B CN 104733726B
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- cobalt acid
- acid manganese
- nanoneedle
- hollow microspheres
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- 239000011572 manganese Substances 0.000 title claims abstract description 35
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 29
- 239000010941 cobalt Substances 0.000 title claims abstract description 29
- 239000004005 microsphere Substances 0.000 title claims abstract description 29
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 28
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 28
- 239000002253 acid Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 13
- 238000010276 construction Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 235000019441 ethanol Nutrition 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000013049 sediment Substances 0.000 claims abstract description 9
- 238000005119 centrifugation Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 21
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007773 negative electrode material Substances 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- -1 Cobalt metal oxide Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000126 substance Substances 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
Abstract
Cobalt acid manganese hollow microspheres and method are prepared the invention provides one kind, by Mn (NO3)2With Co (NO3)2·6H2O is dissolved in deionized water, adds absolute ethyl alcohol, is well mixed；To urea is added in solution, reaction in hydrothermal reaction kettle is transferred to；Centrifugation sediment, with deionized water and ethanol wash, then dries；It is placed in Muffle furnace and rises to 600 DEG C, then be incubated 4 6h calcinings and obtains the hollow microspheres that cobalt acid manganese nanoneedle is assembled into.Cobalt acid manganese hollow microspheres nanoneedle diameter≤30nm is prepared, tiny balloon diameter is at micron order (≤6 μm).Lithium ion battery negative material is used as, due to its special hollow-core construction, improves the cycle performance of lithium ion battery, in 50 200mAg‑1Current density under test performance, discharge capacity is up to 1400mAhg first‑1More than, circulation 25 times afterwards its specific capacity still up to 750mAhg‑1More than.
Description
Technical field
The invention belongs to inorganic nano material synthesis field.In particular, it is related to prepare cobalt acid with mineralizer hydro-thermal method
Hollow microspheres and method that manganese nanoneedle is assembled into.
Background technology
Cobalt acid manganese (MnCo2O4.5) material is the negative material for being applied to lithium ion battery, to the compound gold reported before
Category oxide material is compared discovery, either cycle performance or charge-discharge performance, MnCo2O4.5Performance be all more excellent
's.Compared with simple metal oxide, due to two kinds of complementary and synergies of metal, its capacity is often for metal composite oxide
The theoretical capacity being calculated according to conversion reaction mechanism is higher than, and the electric conductivity of composite oxides is also preferable.Thus,
MnCo2O4.5There is very much the negative material of potentiality to be exploited as lithium ion battery of future generation and receive and attract attention extensively.MnCo2O4.5It is logical
Oxidization-reduction reaction storage lithium, when lithium is embedded in, metal oxide is reduced into metallic crystal (Mn and Co) and is dispersed in lithia base
In body, when lithium is deviate from, they are oxidized to corresponding metal oxide again, thus cobalt manganese composite oxide can inverse theory hold
Measure apparently higher than graphite.Cobalt metal oxide such as CoO capacity is the twice of graphite.Meanwhile, the work electricity of manganese Metal oxide
Press lower and cheap (20 times cheaper than cobalt).Additionally, metal composite oxide is better than simple metal oxide, they
Raising chemical property such as electric conductivity, reversible capacity and stability etc. can be cooperateed with.
Although the composite oxide cathode material of obtained different-shape is with capacity very high at present, its cycle performance
Poor, capacity attenuation is too fast, as the matter of utmost importance for limiting its practical application.Compared to composition identical block materials, nanometer/
Micron-sized hollow oxide specific surface area is big, and lithium ion diffusion length is short, effectively can also alleviate volumetric expansion and cause
Material efflorescence.Thus, prepare hollow Nano/micron level MnCo2O4.5Material, is to prepare efficient MnCo2O4.5Lithium cell negative pole material
One of effective measures of material.
The content of the invention
The purpose of the present invention is, by urea mineralizer hydro-thermal method, to make crystal grain that effective pattern is obtained in growth and control,
There is provided a kind of method for preparing the hollow microspheres that cobalt acid manganese nanoneedle is assembled into.
Cobalt acid manganese hollow microspheres and method are prepared the invention provides one kind, the method is adopted on the basis of hydro-thermal
With environmental protection and the urea that is easy to get as mineralizer, then the cobalt acid manganese hollow microspheres that special construction is obtained by calcining.
Be used as lithium ion battery negative material, due to its special hollow-core construction, can alleviate Lithium-ion embeding abjection during
Volume Changes, are conducive to improving the cycle performance of lithium ion battery, in 50-200mAg-1Current density under test its performance, it is first
Secondary discharge capacity is up to 1400mAhg-1More than, circulation 25 times afterwards its specific capacity still up to 750mAhg-1More than.
Technical side of the invention is as follows：
A kind of method for preparing cobalt acid manganese hollow microspheres, on the basis of hydro-thermal, using urea as mineralizer, leads to
Cross calcining and obtain cobalt acid manganese hollow microspheres.
Comprise the following steps that：
1) is by Mn (NO3)2With Co (NO3)2·6H2O is dissolved in deionized water, is well mixed；Add absolute ethyl alcohol, go from
The volume ratio of sub- water and absolute ethyl alcohol is 1:2-1:0.5；
2) to urea is added in solution, nitrate is 1 with the mol ratio of urea to:5~1:0.5, it is well mixed, Zhi Houzhuan
Move on to reaction in hydrothermal reaction kettle；
3) opens centrifugation sediment after kettle, with deionized water and ethanol wash, is then dried at 60-80 DEG C；
4) will wash dried sediment and be placed in Muffle furnace and rise to 600 DEG C, then be incubated 4-6h calcinings and obtain cobalt acid manganese
The hollow microspheres that nanoneedle is assembled into.
Described step 1) Mn (NO3)2With Co (NO3)2·6H2The mol ratio of O is 1:2.
Described step 2) at a temperature of 90-130 DEG C, the heating response 8-12h in hydrothermal reaction kettle.
Described step 4) heated up with the speed of 1-3 DEG C/min in Muffle furnace.
The present invention prepares cobalt acid manganese hollow microspheres nanoneedle diameter≤30nm, and tiny balloon diameter is in micron order (≤6
μm)。
Cobalt acid manganese hollow microspheres of the invention are used as lithium ion battery negative material.
Promote precipitation synthesis side the invention provides a kind of mineralizer of the cobalt acid manganese hollow microspheres for preparing special construction
Method.With respect to other preparation methods, material has hollow-core construction, and equipment is simple, and technique is easy.
Effect of the invention is：The hollow microspheres that cobalt acid manganese nanoneedle is assembled into, nanoneedle diameter very little can be prepared
(≤30nm), size uniformity, tiny balloon diameter is at micron order (≤6 μm).By the addition of mineralizer urea, significantly improve
The appearance structure of cobalt acid manganese material prepared by hydro-thermal method.Due to the tiny balloon material that obtained material assembles for nanoneedle
Material, is used as lithium ion battery negative material, can significantly alleviate the Volume Changes during Lithium-ion embeding abjection, is conducive to
Improve the cycle performance of lithium ion battery, in 50-200mAg-1Current density under test its performance, discharge capacity is reachable first
1400mAhg-1More than, circulation 25 times afterwards its specific capacity still up to 750mAhg-1More than.In addition, the inventive method has operation
Simply, raw material be easy to get and it is environment-friendly the characteristics of.
Brief description of the drawings
Fig. 1 is MnCo prepared by embodiment 12O4.5Stereoscan photograph, illustrate that prepared product is nanoneedle assembling
Into hollow microsphere structure, nanoneedle diameter very little (≤30nm), size uniformity, tiny balloon diameter is at micron order (≤6 μm).
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 is nanoneedle assembling
Into micro-sphere structure, nanoneedle diameter very little (≤30nm), size uniformity, tiny balloon diameter is at micron order (≤6 μm).
Specific embodiment
Example below proposes preferably to comprise the following steps that：
1) is 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, it is ensured that the volume ratio of deionized water and absolute ethyl alcohol is 1:2-1:0.5, mixing is equal
It is even.
2) to urea is added in solution, nitrate is 1 with the mol ratio of urea to:5~1:0.5, it is well mixed, Zhi Houzhuan
Move on in hydrothermal reaction kettle, 8-12h is heated at a temperature of 90-130 DEG C.
3) opens centrifugation sediment after kettle, is then dried at 60-80 DEG C with deionized water and ethanol wash for several times.
4) be placed in predecessor in Muffle furnace and rise to 600 DEG C with the heating rate of 1-3 DEG C/min by, then is incubated 4-6h calcinings
Obtain the hollow microspheres that cobalt acid manganese nanoneedle is assembled into, nanoneedle diameter very little (≤30nm), size uniformity, tiny balloon
Diameter is at micron order (≤6 μm).
Embodiment 1：
By 0.002molMn (NO3)2, 0.004Co (NO3)2·6H2O is dissolved in 12ml deionized waters, adds the anhydrous second of 24ml
Alcohol, is well mixed.The urea of 0.03mol is added, is well mixed, in transferring the solution into hydrothermal reaction kettle, at a temperature of 90 DEG C
Heating 8h.Centrifugation sediment after kettle is opened, is then dried at 80 DEG C with deionized water and ethanol wash for several times.By forerunner
Thing is placed in Muffle furnace and rises to 600 DEG C with the heating rate of 1 DEG C/min, then is incubated 4h calcinings and obtains cobalt acid manganese nanoneedle and be assembled into
Hollow microspheres.The stereoscan photograph of prepared cobalt acid manganese hollow microspheres is as shown in figure 1, explanation is prepared
Product has hollow-core construction, and is assembled by nanoneedle, nanoneedle diameter very little (≤30nm), size uniformity, tiny balloon
Diameter is at micron order (≤6 μm).In 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-1More than.
Embodiment 2：
By 0.002molMn (NO3)2, 0.004Co (NO3)2·6H2O is dissolved in 18ml deionized waters, adds the anhydrous second of 18ml
Alcohol, is well mixed.The urea of 0.72mol is added, is well mixed, in transferring the solution into hydrothermal reaction kettle, at a temperature of 110 DEG C
Heating 10h.Centrifugation sediment after kettle is opened, is then dried at 70 DEG C with deionized water and ethanol wash for several times.By forerunner
Thing is placed in Muffle furnace and rises to 600 DEG C with the heating rate of 2 DEG C/min, then is incubated 5h calcinings and obtains cobalt acid manganese tiny balloon material
Material.The X-ray diffractogram of prepared cobalt acid manganese hollow microspheres as shown in Fig. 2 the prepared product of explanation have it is pure
Composition.In 100mAg-1Current density under test its performance, discharge capacity is up to 1400mAhg first-1More than, circulate 25 times
Its specific capacity is still up to 750mAhg afterwards-1More than.
Embodiment 3：
By 0.002molMn (NO3)2, 0.004Co (NO3)2·6H2O is dissolved in 24ml deionized waters, adds the anhydrous second of 12ml
Alcohol, is well mixed.The urea of 0.003mol is added, is well mixed, in transferring the solution into hydrothermal reaction kettle, in 130 DEG C of temperature
Lower heating 12h.Centrifugation sediment after kettle is opened, is then dried at 60 DEG C with deionized water and ethanol wash for several times.Will be preceding
Drive thing and be placed in Muffle furnace and rise to 600 DEG C with the heating rate of 3 DEG C/min, then be incubated 6h calcinings and obtain cobalt acid manganese tiny balloon material
Material.The stereoscan photograph of prepared cobalt acid manganese hollow microspheres is as shown in figure 3, the prepared product of explanation is nanoneedle
The hollow microsphere structure being assembled into, nanoneedle diameter very little (≤30nm), size uniformity, tiny balloon diameter is in micron order (≤6
μm).In 50mAg-1Current density under test its performance, discharge capacity is up to 1400mAhg first-1More than, circulation 25 is taken second place
Its specific capacity is still up to 750mAhg afterwards-1More than.
To sum up the accompanying drawing of embodiment can also clearly find out that the product prepared by the present invention is assembled into for cobalt acid manganese nanoneedle
Hollow-core construction microballoon.
Claims (4)
1. cobalt acid manganese (MnCo is prepared2O4.5) hollow-core construction micro-sphere material method, it is characterized in that comprising the following steps that：
1) is by Mn (NO3)2With Co (NO3)2·6H2O is dissolved in deionized water, Mn (NO3)2With Co (NO3)2·6H2The mol ratio of O
It is 1:2, it is well mixed；The volume ratio of addition absolute ethyl alcohol, deionized water and absolute ethyl alcohol is 1:2-1:0.5；
2) to urea is added in solution, nitrate is 1 with the mol ratio of urea to:5~1:0.5, it is well mixed, it is transferred to afterwards
In hydrothermal reaction kettle, at a temperature of 90-130 DEG C, 8-12h reactions are heated in hydrothermal reaction kettle；
3) opens centrifugation sediment after kettle, with deionized water and ethanol wash, is then dried at 60-80 DEG C；
4) will wash dried sediment and be placed in Muffle furnace and rise to 600 DEG C, and heating rate is 1-3 DEG C/min, then is incubated 4-
6h calcinings obtain MnCo2O4.5The hollow-core construction micro-sphere material that nanoneedle is assembled into.
2. the method for claim 1, it is characterized in that preparing MnCo2O4.5Hollow-core construction micro-sphere material nanoneedle diameter≤
30nm, tiny balloon diameter is in micron order.
3. the method for claim 1, it is characterized in that preparing MnCo2O4.5Hollow-core construction microsphere diameter≤6 μm.
4. the method for claim 1, it is characterized in that prepared MnCo2O4.5Hollow-core construction micro-sphere material is used as lithium ion
Cell negative electrode material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105895896A (en) * | 2015-07-20 | 2016-08-24 | 合肥国轩高科动力能源有限公司 | Positive electrode material of lithium ion battery and preparation method of positive electrode material |
| 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 |
| CN106711443B (en) * | 2016-12-16 | 2019-07-12 | 中南大学 | A kind of shuttle shape cobalt acid manganese material and its preparation and application |
| CN108238648B (en) * | 2018-03-26 | 2019-12-24 | 淮北师范大学 | Preparation method of lithium ion battery negative electrode material |
| CN109119251B (en) * | 2018-08-30 | 2020-04-24 | 中北大学 | Porous MnCo2O4．5Preparation method of electrode material |
| CN109524636A (en) * | 2018-09-30 | 2019-03-26 | 肇庆市华师大光电产业研究院 | A kind of lithium ion battery negative material and preparation method thereof |
| CN110436530A (en) * | 2019-07-18 | 2019-11-12 | 镇江博润新材料有限公司 | A kind of yolk shell structure cobalt acid manganese porous microsphere and preparation method thereof |
| CN112661198A (en) * | 2020-12-25 | 2021-04-16 | 北京理工大学 | Method for preparing potassium ion battery electrode material by using waste lithium ion battery |
| CN114335472A (en) * | 2021-12-30 | 2022-04-12 | 燕山大学 | Cobalt-manganese bimetallic MOFs derivative material and preparation method and application thereof |
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| CN102491756B (en) * | 2011-11-16 | 2015-03-18 | 重庆仪表材料研究所 | Method for preparing nanoscale thermosensitive powder by hydrothermal method |
| CN103746104A (en) * | 2013-12-09 | 2014-04-23 | 中国科学院福建物质结构研究所 | Manganese cobalt oxide self-assembled micro-spheres, and preparation and applications thereof |
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