CN109830672A - A kind of Preparation method and use of the porous carbon nano-complex of MnO N doping - Google Patents
A kind of Preparation method and use of the porous carbon nano-complex of MnO N doping Download PDFInfo
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- CN109830672A CN109830672A CN201910208431.XA CN201910208431A CN109830672A CN 109830672 A CN109830672 A CN 109830672A CN 201910208431 A CN201910208431 A CN 201910208431A CN 109830672 A CN109830672 A CN 109830672A
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- 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 preparation methods of porous carbon nano-complex of MnO N doping, include the following steps: to be dissolved in trimesic acid in 80 DEG C of deionized waters, constant temperature water bath is for a period of time, then manganese acetate is dissolved in deionized water, acetic acid manganese solution is then poured into constant temperature in trimesic acid solution to stir, isothermal reaction is for a period of time afterwards cleaned it, is centrifuged, and metal-organic framework object, i.e. Mn-BTC powder can be obtained；Mn-BTC powder is dry in freeze-day with constant temperature baking oven；Mn-BTC powder is calcined in ammonia atmosphere, obtains the porous carbon nano-complex of MnO N doping；The porous carbon nano-complex of MnO N doping shows excellent chemical property in lithium ion storage, and volume expansion problem of manganese oxide during lithiumation can be effectively relieved in porous carbon.
Description
Technical field
The present invention relates to field of nanocomposite materials, and in particular to and it is a kind of using metal-organic framework object as presoma, in conjunction with
Ammonia atmosphere calcination processing is to obtain the preparation method of the porous carbon nano-complex of MnO N doping and be applied to high property
The negative electrode material of energy lithium ion battery.
Background technique
Capacity of lithium ion battery is big, operating voltage is high, self discharge is low, it is highly-safe, have extended cycle life, memory-less effect,
It is small in size, light-weight, specific energy is high, and is free of the heavy metal harmful substance of cadmium, lead, mercury etc, therefore such ring will not be generated
Border pollution.In recent years, the high speed development of portable electronic device, electric tool and electric vehicle engineering is to lithium ion battery
More stringent requirements are proposed for performance, to excite the lithium ion battery negative material of height ratio capacity of new generation, long circulation life
Research.Compared with the carbons negative electrode material of current commercialization, manganese oxide negative electrode material theoretical specific capacity with higher and energy
Density, therefore be considered as potential next-generation lithium ion battery negative material.But manganese oxide negative electrode material is in charge and discharge
Huge volume change is produced in cyclic process, this will lead to the collapse of the crushing of electrode material and electrodes conduct network,
To make cycle performance sharp-decay.By constructing specific manganese oxide nanometer material and carrying out N doping porous carbon packet to it
It covers, the cycle life of manganese oxide negative electrode material can be improved to a certain extent.But research both domestic and external does not still have at present
It is fully solved the above problem.Therefore, the manganese oxide nanometer anode material of modification is further designed and prepared, lithium ion is improved
The charge-discharge performance of cell negative electrode material is of great significance.
Metal-organic framework object is a kind of with periodical frame structure holey material, has high specific surface area.
Using metal-organic framework object as presoma, both had in conjunction with the porous carbon nano-composite material of MnO N doping that calcination processing obtains
There is the performance advantage of single phase metal oxide, and assigns the performance that its single phase metal oxide does not have, while having benefited from gold
The unique structure of category-organic framework, so that this nanocomposite has high specific surface area, with this nanocomposite structure
The lithium ion battery built can effectively improve its lithium electrical property.
Summary of the invention
The present invention is to provide a kind of MnO@N doping porous carbon to avoid above-mentioned existing deficiencies in the technology
The Preparation method and use of nano-complex, it is intended to improve the cyclical stability and cyclic specific capacity of material.
The present invention solves technical problem, the invention provides the following technical scheme:
A kind of preparation method of the porous carbon nano-complex of MnO N doping, includes the following steps:
(1) trimesic acid is dissolved in 80 DEG C of deionized waters, manganese acetate for a period of time, is then dissolved in by constant temperature water bath
In ionized water, acetic acid manganese solution is then poured into constant temperature in trimesic acid solution and is stirred, isothermal reaction is for a period of time afterwards to it
It cleaned, be centrifuged, metal-organic framework object, i.e. Mn-BTC powder can be obtained；
(2) Mn-BTC powder obtained above is dry in freeze-day with constant temperature baking oven；
(3) step (2) Mn-BTC powder is calcined in ammonia atmosphere, it is nano combined obtains MnO@N doping porous carbon
Object.
In step (1), the molar concentration rate of manganese acetate and trimesic acid is 1~4, and bath temperature is 80~100 DEG C, instead
It is 30~60 minutes between seasonable.
In step (2), thermostatic drying chamber temperature is 80 DEG C.
In step (3), the porous carbon nano-complex of MnO is calcined in ammonia atmosphere, and calcination condition is equal are as follows: calcination temperature
800 DEG C, soaking time 2 hours, heating rate was 2 DEG C/min.
A kind of purposes of the porous carbon nano-complex of MnO, the negative electrode material for high performance lithium ion battery.
Compared with the prior art, the beneficial effects of the present invention are embodied in:
1, the present invention is using metal-organic framework object as presoma, using the high feature of its specific surface area, in conjunction with electron transfer
The high porous carbon of rate can obtain the better porous carbon nano-composite material of MnO N doping of chemical property；
2, preparation method of the invention is quick and easy, and mixed solution quickly forms presoma with vigorous stirring；Then exist
In ammonia after calcination process, the porous carbon nano-composite material of MnO N doping is obtained.
3, porous carbon provides a large amount of holes and adjusts volume expansion and contraction of the metal oxide in electrochemical reaction, this
Method not only solves metal oxide in cyclic process the problem of structural instability, while providing a large amount of holes to solve
The problem of crossing the volume expansion and contraction of metal oxide,
4, N doping can effectively improve the electric conductivity of porous carbon and increase the electro-chemical activity site of storage lithium, further increase
Electrochemical lithium storage performance is added.
Detailed description of the invention
Fig. 1 is the SEM photograph of the 1 porous carbon nano-complex of gained MnO N doping of the embodiment of the present invention；
Fig. 2 is the TEM photo of the 1 porous carbon nano-complex of gained MnO N doping of the embodiment of the present invention；
Fig. 3 is the EDS photo of the porous carbon nano-complex of MnO N doping in the embodiment of the present invention 1；
Fig. 4 is the SEM photograph of the 2 porous carbon nano-complex of gained MnO of the embodiment of the present invention；
Fig. 5 is the TEM photo of the 2 porous carbon nano-complex of gained MnO of the embodiment of the present invention；
Fig. 6 is the EDS photo of the porous carbon nano-complex of MnO in the embodiment of the present invention 2；
Fig. 7 is that the porous carbon nano-complex of MnO of the embodiment of the present invention 2 and embodiment 1 and MnO N doping porous carbon are received
The XRD photo of rice compound；
Fig. 8 is the high rate performance of the porous carbon nano-complex of MnO N doping in the embodiment of the present invention 1；
Fig. 9 is the high rate performance of the porous carbon nano-complex of MnO in the embodiment of the present invention 2.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
Agents useful for same, material etc. unless otherwise specified, commercially obtain in the following example.
Battery performance test is all made of blue electric battery test system in following embodiments, by gained cathode in following embodiments
Composite material, conductive black and PVDF are that slurries are made in uniformly mixed be dissolved in nmp solution of 80:10:10 according to mass ratio, so
It is equably applied in copper foil current collector afterwards and working electrode is made, glass fibre membrane is diaphragm, and electrolyte is binary electrolyte, is being filled
2032 button cells are assembled into full argon gas glove box, test voltage range is 0.01V-3Vvs Li+/Li。
The preparation method of embodiment 1, the porous carbon nano-complex of MnO N doping, includes the following steps:
(1) 0.428g trimesic acid is added in 80 DEG C of deionized waters of 50ml, constant temperature water bath for a period of time, to it
It is completely dissolved, 0.495g manganese acetate is added in 80 DEG C of deionized waters of 50ml, and acetic acid manganese solution is poured into trimesic acid solution
In, constant temperature is stirred to react 30 minutes, obtains metal-organic framework object presoma, i.e. Mn-BTC powder；
(2) Mn-BTC powder obtained above is dry in freeze-day with constant temperature baking oven, thermostatic drying chamber temperature is 80 DEG C；
(3) metal-organic framework object presoma obtained by (1) is calcined in ammonia atmosphere, 800 DEG C of calcination temperature, heat preservation
Time 2 h, heating rate are 2 DEG C/min, can be obtained the porous carbon nano-complex of MnO N doping.
The preparation of the porous carbon nano-complex of embodiment 2, MnO
Metal-organic framework object presoma obtained by (1) in embodiment 1 is calcined in argon atmosphere, calcination temperature 800
DEG C, soaking time 2 hours, heating rate was 2 DEG C/min, can be obtained the porous carbon nano-complex of MnO；
Fig. 1 and Fig. 2 is SEM the and TEM photo of the 2 porous carbon nano-complex of gained MnO N doping of above-described embodiment, can
To find out material diameter between 200-400nm.
Fig. 3 and Fig. 4 is the porous carbon nano-complex SEM of MnO and TEM photo obtained in embodiment 2, it can be seen that material
Material is solid nano wire, and has porous structure.
Fig. 5 is the EDS image of 1 gained sample of embodiment, it can be seen that metal-organic framework object presoma is passing through ammonia
In atmosphere calcine after, in product include a large amount of nitrogen, nitrogen doped be conducive to basis material electric conductivity raising, and
The electro-chemical activity site for increasing storage lithium, further increases electrochemical lithium storage performance.
Fig. 6 is the EDS image of 2 gained sample of embodiment.
Fig. 7 be in embodiment 2 gained embodiment 1 in the porous carbon nano-complex of MnO N doping and MnO porous carbon nanometer
The XRD diagram of compound, by the comparison at two groups of peaks in figure it is found that the diffraction maximum of two groups of samples all meets carbon and the characteristic peak of MnO.
Fig. 8 and Fig. 9 is respectively the chemical property figure of 2 gained composite material of embodiment 1 and embodiment.It can be seen that implementing
The chemical property of the formation porous carbon nano-complex of MnO N doping of example 1.As can be seen that being returned to by 60 charge and discharge
Battery still keeps 800mAh g after the current density of 0.1A/g-1Height ratio capacity, therefore battery is functional.And embodiment
2 obtain is the porous carbon nano-complex of MnO, battery is only after 60 charge and discharge are returned to the current density of 0.1A/g
Only keep 670mAh g-1Specific capacity, therefore, the porous carbon nano-complex of MnO N doping of the invention is a kind of excellent lithium
Ion battery cathode material.
Claims (5)
1. a kind of preparation method of the porous carbon nano-complex of MnO N doping, which comprises the steps of:
(1) trimesic acid is dissolved in 80 DEG C of deionized waters, manganese acetate for a period of time, is then dissolved in deionization by constant temperature water bath
In water, acetic acid manganese solution is then poured into constant temperature in trimesic acid solution and is stirred, isothermal reaction for a period of time afterwards carries out it
Cleaning, centrifugation, can be obtained metal-organic framework object, i.e. Mn-BTC powder；
(2) Mn-BTC powder obtained above is dry in freeze-day with constant temperature baking oven；
(3) step (2) Mn-BTC powder is calcined in ammonia atmosphere, obtains the porous carbon nano-complex of MnO N doping.
2. a kind of preparation method of porous carbon nano-complex of MnO N doping according to claim 1, it is characterised in that:
In step (1), the molar concentration rate of manganese acetate and trimesic acid is 1~4, and bath temperature is 80~100 DEG C, when reaction
Between be 30~60 minutes.
3. a kind of preparation method of porous carbon nano-complex of MnO N doping according to claim 1, it is characterised in that:
In step (2), thermostatic drying chamber temperature is 80 DEG C.
4. a kind of preparation method of porous carbon nano-complex of MnO N doping according to claim 1, it is characterised in that:
In step (3), the porous carbon nano-complex of MnO is calcined in ammonia atmosphere, and calcination condition is equal are as follows: calcination temperature 800
DEG C, soaking time 2 hours, heating rate was 2 DEG C/min.
5. a kind of purposes of the porous carbon nano-complex of MnO N doping, it is characterised in that: for high performance lithium ion battery
Negative electrode material.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110212194A (en) * | 2019-06-12 | 2019-09-06 | 合肥工业大学 | A kind of preparation method and applications of one-dimensional MOF@ZIF core-shell structure |
| CN110364712A (en) * | 2019-07-15 | 2019-10-22 | 合肥工业大学 | A kind of preparation method and applications of porous carbon@N doping porous carbon core-shell structure |
| CN111389445A (en) * | 2020-04-28 | 2020-07-10 | 润泰化学股份有限公司 | Composite solid acid catalyst for preparing 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate and preparation method thereof |
| CN111841617A (en) * | 2020-08-25 | 2020-10-30 | 南京大学 | Mn (manganese)2O3@ N doped porous carbon hybrid Fenton material and preparation method and application thereof |
| CN115331978A (en) * | 2022-09-02 | 2022-11-11 | 河北工业大学 | Preparation method and application of positive and negative electrode matching material of lithium ion hybrid capacitor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107732171A (en) * | 2017-09-19 | 2018-02-23 | 宿州学院 | One-dimensional porous carbon coating manganese monoxide combination electrode material and preparation method |
-
2019
- 2019-03-19 CN CN201910208431.XA patent/CN109830672A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107732171A (en) * | 2017-09-19 | 2018-02-23 | 宿州学院 | One-dimensional porous carbon coating manganese monoxide combination electrode material and preparation method |
Non-Patent Citations (4)
| Title |
|---|
| LINGJUN KONG，ET AL.: ""Nitrogen-Doped Wrinkled Carbon Foils Derived from MOF Nanosheets for Superior Sodium Storage"", 《ADV. ENERGY MATER.》 * |
| PANPAN SU，ET AL.: ""Nitrogen-doped carbon nanotubes derived from Zn-Fe-ZIF nanospheres and their application as efficient oxygen reduction electrocatalysts with in situ generated iron species"", 《CHEMICAL SCIENCE》 * |
| XIAOJIE ZHANG，ET AL.: ""MnO@C nanorods derived from metal-organic frameworks as anode for superiorly stable and long-life sodium-ion batteries"", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| 池琴等: ""氮掺杂碳包覆MnO 纳米棒的制备及电化学性能研究"", 《2015年第十四届全国应用化学年会论文集(上)》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110212194A (en) * | 2019-06-12 | 2019-09-06 | 合肥工业大学 | A kind of preparation method and applications of one-dimensional MOF@ZIF core-shell structure |
| CN110212194B (en) * | 2019-06-12 | 2021-01-08 | 合肥工业大学 | Preparation method and application of one-dimensional MOF @ ZIF core-shell structure |
| CN110364712A (en) * | 2019-07-15 | 2019-10-22 | 合肥工业大学 | A kind of preparation method and applications of porous carbon@N doping porous carbon core-shell structure |
| CN111389445A (en) * | 2020-04-28 | 2020-07-10 | 润泰化学股份有限公司 | Composite solid acid catalyst for preparing 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate and preparation method thereof |
| CN111841617A (en) * | 2020-08-25 | 2020-10-30 | 南京大学 | Mn (manganese)2O3@ N doped porous carbon hybrid Fenton material and preparation method and application thereof |
| CN111841617B (en) * | 2020-08-25 | 2021-10-19 | 南京大学 | Mn (manganese)2O3@ N doped porous carbon hybrid Fenton material and preparation method and application thereof |
| CN115331978A (en) * | 2022-09-02 | 2022-11-11 | 河北工业大学 | Preparation method and application of positive and negative electrode matching material of lithium ion hybrid capacitor |
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