CN109574078A - A kind of manganese monoxide nano particle and its application and preparation method - Google Patents
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Abstract
The present invention provides a kind of manganese monoxide nano particles.The manganese monoxide nano particle has core-shell structure, can be applied to prepare Zinc ion battery anode.The anode can be applied to prepare Zinc ion battery.The present invention also provides a kind of preparation methods of manganese monoxide nano particle.The preparation method is that manganese source and imidazolium compounds, i.e., be separately added into distilled water by the precipitation method, stirring to dissolution, then be sufficiently mixed.Continue to stir a few hours, obtains yellowish-brown suspension solution.Material is repeatedly washed, after centrifugation, is dried to obtain presoma in an oven, obtains uniform manganese monoxide nano particle after sintering.The molecular formula of the manganese monoxide nano particle is MnO.The manganese monoxide nano particle has excellent cyclical stability and good specific energy density performance, and reaction condition is mild, simple process, suitable for mass production.
Description
Technical field
The invention belongs to high energy Zinc ion battery positive electrode and its preparation technical fields, and in particular to a kind of manganese monoxide
Nano particle and its application and preparation method.
Background technique
Zinc ion battery is a kind of new secondary battery of rising in recent years, with high-energy density, high power density,
The features such as battery material is nontoxic, cheap, preparation process is simple.It is very high using valence that this has it in large-scale energy storage field
Value and development prospect.More attracting to be, zinc ion has divalent charge, this allows Zinc ion battery to provide higher deposit
Store up capacity.The environment-friendly type aqueous electrolyte with high ionic conductivity also can be used in Zinc ion battery.
In existing Zinc ion battery positive electrode, Mn oxide is since its reserves is big, price is low, toxicity is low, manganese element
Valence state is more, it is considered to be most potential positive electrode.But it is existing research concentrate on high-valence state basis Mn oxide zinc from
Application in sub- anode.For example, various polymorphic MnO2With different reaction mechanism [J.Am.Chem.Soc., 2017,
139].Manganese sesquioxide managnic oxide also shows excellent zinc ion storage performance [Electrochim.Acta, 2017,229].However,
The ionic conductivity and electronic conductivity of these Mn oxides are low, limit its chemical property.Therefore, new there is an urgent need to explore
Positive electrode promote the charge and discharge of divalent zinc ion.
Past ZnMn (III)2O4The vacancy of manganese is Zn in spinelle2+The diffusion and migration of ion are made that contribution, this
It provides feasible explores and is based on lower valency valence Mn oxide as the positive extreme direction of Zinc ion battery.Manganese monoxide nanometer
The manganese divalent that is positive is difficult to continue to be embedded in zinc ion and be reduced in grain Mn (II) O, but introduces manganese in manganese monoxide nano particle
Vacancy, manganese valence are increased to trivalent or tetravalence, so that manganese monoxide nano particle has storage zinc performance.However, at present not
Research about MnO as water system Zinc ion battery positive electrode.
In research of the past to Mn-based material, charge-discharge cycle process of the almost all of Mn-based material in Zinc ion battery
In can generate phase transformation, there is the variation of structure.This structure change can make material volume acute variation to make structural breakdown.
Summary of the invention
The first purpose of the invention is to provide a kind of manganese monoxide nano particle with core-shell structure.One oxidation
Manganese nano particle structure during Chu Xinshi, zinc ion deintercalation does not change.The stabilization of its structure facilitates material can be
Good performance is obtained during long circulating.
A second object of the present invention is to provide a kind of manganese monoxide nano particles in water system Zinc ion battery anode
Application.
Third object of the present invention is to provide a kind of application of Zinc ion battery anode in water system Zinc ion battery.
Fourth object of the present invention is to provide a kind of preparation method of manganese monoxide nano particle.
A kind of manganese monoxide nano particle of the present invention, has core-shell structure.
Inventors discovered through research that heretofore described manganese monoxide nano particle manganese in electrolyte during the charging process
Ion concentration increases, while valence state increases Mn element after charging, and manganese ion is deviate from from material matrix, forms manganese vacancy,
Structure does not change and enables material in length during zinc ion deintercalation when providing more zinc storage sites, and storing up zinc
Good performance is obtained in cyclic process, this facilitates the chemical property for promoting material.
Inventor is by research it has furthermore been found that the non-original of manganese monoxide nano particle of the invention in such as charge and discharge process
Shown in the XRD spectrum of position, the manganese monoxide nano particle does not have structured change during deintercalation zinc ion, maintains good
Good structural stability.
In the core-shell structure, the diameter of core is 20nm~70nm, shell with a thickness of 4nm~10nm.
The manganese monoxide nano particle of core is constituted in the core-shell structure and constitutes the crystalline substance of the manganese monoxide nano particle of shell
Planar orientation is different.Inventor it is thought that due to using glyoxaline compound different complexing sites caused by, high preferred orientation
It is different to advantageously forming core-shell structure.
The partial size of the manganese monoxide nano particle is 30~80nm.
A kind of preparation method of manganese monoxide nano particle, includes the following steps:
It is mixed, is centrifuged after manganese source and complexant are dissolved in water respectively, it is dry, presoma is obtained, under protective atmosphere
Sintering, obtains the manganese monoxide nano particle.
The manganese source is manganese salt.Preferably, the manganese salt is manganous salt；
It is highly preferred that the manganese salt includes Mn (NO3)2, MnCl2, Mn (AC)2And MnSO4One or more of mixing
Object.
The complexant includes glyoxaline compound.The glyoxaline compound can preferably be such that the manganese element of divalent aoxidizes
Glyoxaline compound.Preferably, the glyoxaline compound is preferably methylimidazole class compound.
The glyoxaline compound includes 2-methylimidazole, 4-methylimidazole, imidazoles and 1, in 2- methylimidazole
It is one or more of.
The concentration of manganese source solution is 0.01-0.1mol/L.
Glyoxaline compound solution concentration is 0.1~1mol/L.
Manganese source and the molar ratio of glyoxaline compound are 1:5~1:9.
The time of the stirring is 2-12h.
Dry temperature is 50-70 DEG C.The dry time is 8-14 hours.
The temperature of the sintering is 450-550 DEG C.The preferred time is 1-6 hours.Heating rate is 1-10 DEG C/min.
The sintering protective atmosphere is hydrogen-argon-mixed or argon gas.
The present invention can be such that the manganese element of divalent aoxidizes by glyoxaline compound, obtain mangano-manganic oxide presoma.Atmosphere
Mangano-manganic oxide presoma is reduced in sintering process, obtains the manganese monoxide nano particle.
Preparation method of the present invention is the precipitation method, is that manganese source and glyoxaline compound are separately added into Yu Shuizhong, stirring
To dissolution, then it is sufficiently mixed；Continue to stir, obtains yellowish-brown suspension solution；Material is repeatedly washed, after centrifugation, (in baking oven
In) it is dried to obtain presoma；Manganese monoxide Nanoparticulate material is obtained after sintering.The manganese monoxide material molecule formula is
MnO.The manganese monoxide positive electrode of this method preparation is to be applied to preparation water system Zinc ion battery positive electrode for the first time, is had excellent
Different cyclical stability and good specific energy density performance, and reaction condition is mild, simple process, it is suitable for mass production.
Manganese monoxide nano particle obtained by the present invention can be applied to preparation water system Zinc ion battery anode.
Manganese monoxide nano particle obtained by the present invention can be applied to preparation water system Zinc ion battery.
The present invention has synthesized the manganese monoxide nanometer of uniform morphology with core-shell structure by a kind of simple method
Grain, and it is applied to preparation water system Zinc ion battery anode.It is first right to find in the charge and discharge process of manganese monoxide nano particle
Battery charges, and material can generate manganese vacancy in first circle charging process, is zinc ion while improving zinc ion kinetics of diffusion
Storage provide more active sites, facilitate promoted material chemical property.
Manganese monoxide nano particle provided by the invention, for Chu Xinshi, structure does not change during zinc ion deintercalation
Become.The stabilization of structure facilitates material can obtain good performance during long circulating.And relative to other zinc ions electricity
For the positive electrode in pond, manganese monoxide nano-particle material provided by the invention has outstanding specific energy density,
135.6W kg-1Under conditions of can keep 356.86Wh kg-1Specific energy, and cyclical stability with higher, capacity retention ratio
It is very high.
In conclusion compared with the prior art, the invention has the following advantages:
Manganese monoxide nano particle of the present invention structure during storing up zinc does not change, and has good stability,
The commercialization for promoting Zinc ion battery is had a very important significance.
Water system Zinc ion battery anode structure of the present invention is stable, specific capacity is high, has superior cyclical stability and height
Specific energy performance.
The synthetic method of manganese monoxide nano particle of the present invention is simple, low in cost, and manganese monoxide nano particle
Material non-toxic environmental protection, has a good application prospect in scale energy storage field；It can be used for large-scale industrial production.
Detailed description of the invention
Fig. 1 is (a) XRD spectrum of the manganese monoxide nano particle in embodiment 1；(b) the xps energy spectrum figure of Mn3s track；
(c) Raman map.
Fig. 1 (a) is the XRD spectrum of the embodiment of the present invention 1.As can be seen from Fig., MnO has been prepared in embodiment.Fig. 1
(b) be manganese monoxide nano particle Mn3s track prepared by embodiment 1 xps energy spectrum figure.As can be seen from the figure manganese monoxide
Mn in nano particle is positive divalent.Fig. 1 (c) is the Raman map of manganese monoxide nano particle prepared by embodiment 1.
Fig. 2 is (a) SEM figure of the manganese monoxide nano particle in embodiment 1；(b) TEM schemes；(c) EDS distribution diagram of element.
Fig. 2 (a) is the scanning electron microscopic picture of manganese monoxide nano-particle material prepared by embodiment 1, can be turned round from figure
Manganese monoxide nano particle has uniform nanoparticles structure and morphology out.Sample prepared by embodiment 1 is shown in Fig. 2 (b)
Transmission electron microscope picture, it can be seen from the figure that the size of manganese monoxide nano granule piece be 30-80nm.Its nucleocapsid knot
In structure, the diameter of core is 20nm to 70nm, shell with a thickness of 4nm to 10nm.
The EDS distribution diagram of element of manganese monoxide nano-particle material prepared by embodiment 1 is shown in Fig. 2 (c), illustrates material
Material is uniform manganese monoxide nano-particle material, has a small amount of Carbon deposition in the material.Fig. 3 is one in embodiment 1
The HRTEM of manganese oxide nano granule schemes.
Fig. 3 is that the high-resolution TEM of MnO nano particle schemes, from the MnO crystal that can be clearly seen in core and shell structure in figure
In the presence of orientation difference.
Fig. 4 is (a) cyclic voltammetry curve of the carbon containing manganese monoxide nano particle in embodiment 1；(b)100mA g-1Fill
Discharge cycle performance and charging and discharging curve；(c)1000mA g-1Charge-discharge performance.
Manganese monoxide nano-particle material prepared by embodiment 1 is as anode, and zinc metal is as cathode, 2MZnSO4+
0.1M MnSO4Solution uses glass fibre membrane as electrolyte, diaphragm.The constant current charge-discharge experiment of battery uses at room temperature
The Land CT2001A equipment of Wuhan Lan electricity company is tested.Test voltage range is 0.8~1.8V, and reference is in Zn/Zn2+。
The chemical property of the carbon containing manganese monoxide nano-particle material of the preparation of embodiment 1 is shown in Fig. 4.Wherein,
Fig. 4 (a) is cyclic voltammetry curve；(b)100mA g-1Charge-discharge performance and charging and discharging curve；(c)1000mA g-1's
Charge-discharge performance.It can be seen from the figure that the manganese monoxide nano particle that embodiment 1 obtains is in 100mA g-1Lower maximum is put
Electric specific capacity is 310mA h g-1, there is high specific discharge capacity.Have stable charge and discharge platform and superior circulation steady simultaneously
It is qualitative (such as in 1000mA g-1Current density under, recycle up to 1500 times, capacitance loss is seldom).This illustrates the manganese monoxide
Nano-particle material has excellent chemical property.
Mn/Zn rubs in (a) electrolyte when Fig. 5 is the first circle charge and discharge of the carbon containing manganese monoxide nano particle in embodiment 1
That ratio；(b)Mn2p3/2The xps energy spectrum figure of track.
Fig. 5 (a) is electrolysed when carbon containing manganese monoxide nano-particle material first circle charge and discharge prepared by embodiment 1 are shown
Mn/Zn molar ratio in liquid.Mn ion concentration increases in electrolyte after charging as we can see from the figure, this illustrates first circle Mn ion
Deviate from into electrolyte.Mn2p when Fig. 5 (b) is first circle charge and discharge3/2The xps energy spectrum figure of track, Mn element is filling as the result is shown
Valence state increases after electricity, illustrates that manganese ion is deviate from from material matrix, forms manganese vacancy.
Fig. 6 is the ex situ XRD spectrum of manganese monoxide nano particle in charge and discharge process in embodiment 1.
The ex situ XRD diagram for the manganese monoxide nano particle that embodiment 1 in charge and discharge process is prepared is shown in Fig. 6
Spectrum.It can be seen from the figure that manganese monoxide nano particle substance in charge and discharge process does not have cenotype generation and former face-centered cubic
Structure is constant.
Fig. 7 is the XRD spectrum of (a) presoma mangano-manganic oxide and manganese monoxide nano particle in embodiment 2；(b)
100mA g-1Charge-discharge performance.
Fig. 7 (a) is the XRD spectrum of the embodiment of the present invention 2.As can be seen from Fig., embodiment be prepared it is pure before
Drive body Mn3O4And MnO.Fig. 7 (b) is the 100mA g of the manganese monoxide nano particle in embodiment 2-1Charge-discharge performance.
The manganese monoxide nano particle that embodiment 2 obtains initial discharge specific capacity with higher.
Fig. 8 is the XRD spectrum of (a) presoma mangano-manganic oxide and manganese monoxide nano particle in embodiment 3；(b)
100mA g-1Charge-discharge performance.
Fig. 8 (a) is the XRD spectrum of the embodiment of the present invention 3.As can be seen from Fig., embodiment be prepared it is pure before
Drive body Mn3O4And MnO.Fig. 8 (b) is the 100mA g of the manganese monoxide nano particle in embodiment 3-1Charge-discharge performance.
The manganese monoxide nano particle that embodiment 3 obtains has good cyclical stability.
Fig. 9 is the XRD spectrum of (a) presoma mangano-manganic oxide and manganese monoxide nano particle in embodiment 4；(b)
100mA g-1Charge-discharge performance.
Fig. 9 (a) is the XRD spectrum of the embodiment of the present invention 4.As can be seen from Fig., embodiment be prepared it is pure before
Drive body Mn3O4And MnO.Fig. 9 (b) is the 100mA g of the manganese monoxide nano particle in embodiment 4-1Charge-discharge performance.
Figure 10 is the XRD spectrum of the manganese monoxide nano particle in embodiment 5.As can be seen from Fig., embodiment is prepared into
Pure MnO is arrived.
Specific embodiment
It is intended to further illustrate the present invention with reference to embodiments, is not intended to limit the present invention.
Embodiment 1
By 2mmol Mn (NO3)2It is respectively separately added into the distilled water of 40mL with 1.3g methylimidazole, in room temperature condition
Under be stirred to dissolution, later by Mn (NO3)2Solution pours into methylimidazole solution, and solution changes colour rapidly, continues in room temperature item
4h is stirred under part, after obtaining suspension centrifuge washing, then 60 DEG C of dryings in an oven, obtain persursor material.Through Ar/H2
Uniform manganese monoxide Nanoparticulate material is obtained after the lower 550 degrees Celsius of sintering of mixed atmosphere.
Manganese monoxide nano-particle material prepared by the present embodiment 1 is as anode, and zinc metal is as cathode, 2MZnSO4+
0.1M MnSO4Solution uses glass fibre membrane as electrolyte, diaphragm.The constant current charge-discharge experiment of battery uses at room temperature
The Land CT2001A equipment of Wuhan Lan electricity company is tested.Test voltage range is 0.8~1.8V, and reference is in Zn/Zn2+.Electrically
Energy result is referring to Fig. 3
Embodiment 2
By 2mmol MnCl2It is respectively separately added into the distilled water of 40mL with 1.3g methylimidazole, at room temperature
It is stirred to dissolution, later by MnCl2Solution pours into methylimidazole solution, and solution changes colour rapidly, continues at room temperature
12h is stirred, after obtaining suspension centrifuge washing, then 60 DEG C of dryings in an oven, obtain persursor material Mn3O4.Through Ar/
H2Uniform manganese monoxide Nanoparticles Nanoparticles shape material is obtained after the lower 550 degrees Celsius of sintering of mixed atmosphere.
Embodiment 3
By 2mmol MnSO4It is respectively separately added into the distilled water of 40ml with 1.3g methylimidazole, at room temperature
It is stirred to dissolution, later by MnSO4Solution pours into methylimidazole solution, and solution changes colour rapidly, continues at room temperature
12h is stirred, after obtaining suspension centrifuge washing, then 60 DEG C of dryings in an oven, obtain persursor material Mn3O4.Through Ar/
H2Uniform manganese monoxide Nanoparticles Nanoparticles shape material is obtained after the lower 550 degrees Celsius of sintering of mixed atmosphere.
Embodiment 4
By 2mmol Mn (AC)2It is respectively separately added into the distilled water of 40ml with 1.3g methylimidazole, in room temperature condition
Under be stirred to dissolution, later by Mn (AC)2Solution pours into methylimidazole solution, and solution changes colour rapidly, continues in room temperature item
4h is stirred under part, after obtaining suspension centrifuge washing, then 60 DEG C of dryings in an oven, obtain persursor material Mn3O4.Through
Ar/H2Uniform manganese monoxide Nanoparticles Nanoparticles shape material is obtained after the lower 550 degrees Celsius of sintering of mixed atmosphere.
Embodiment 5
By 2mmol Mn (NO3)2It is respectively separately added into the distilled water of 40ml with 1.3g imidazoles, stirs at room temperature
To dissolution, later by Mn (NO3)2Solution pours into imidazole solution, and solution changes colour rapidly, and 8h is stirred in continuation at room temperature, will
After obtaining suspension centrifuge washing, then 60 DEG C of dryings in an oven.Through Ar/H2After the lower 550 degrees Celsius of sintering of mixed atmosphere
To uniform manganese monoxide Nanoparticles Nanoparticles shape material.
Claims (10)
1. a kind of manganese monoxide nano particle, it is characterised in that: the nano particle has core-shell structure.
2. manganese monoxide nano particle according to claim 1, it is characterised in that: the diameter of the core is 20~70nm,
The shell with a thickness of 4~10nm.
3. manganese monoxide nano particle according to claim 2, which is characterized in that constitute the one of core in the core-shell structure
The high preferred orientation of manganese oxide nano granule and the manganese monoxide nano particle for constituting shell is different.
4. manganese monoxide nano particle according to claim 1-3, it is characterised in that: the manganese monoxide nanometer
The partial size of particle is 30~80nm.
5. a kind of preparation method of manganese monoxide nano particle, which comprises the steps of:
It is mixed, is centrifuged after manganese source and complexant are dissolved in water respectively, it is dry, presoma is obtained, is burnt under protective atmosphere
Knot obtains manganese monoxide nano particle.
6. the preparation method of manganese monoxide nano particle according to claim 5, it is characterised in that: the manganese source uses
Be manganese salt；Preferably, the manganese salt is manganous salt；It is highly preferred that the manganese salt includes Mn (NO3)2, Mn (AC)2,
MnCl2And MnSO4One or more of mixture.
7. the preparation method of manganese monoxide nano particle according to claim 5, it is characterised in that: the complexant packet
Include glyoxaline compound；The glyoxaline compound that the glyoxaline compound can preferably be such that the manganese element of divalent aoxidizes；It is excellent
Selection of land, the glyoxaline compound are preferably methylimidazole class compound；Preferably, the glyoxaline compound is preferred
Including 2-methylimidazole, 4-methylimidazole, imidazoles and 1, one or more of 2- methylimidazole.
8. the preparation method of manganese monoxide nano particle according to claim 5, it is characterised in that: preferably, manganese source is molten
The concentration of liquid is 0.01-0.1mol/L；
Preferably, the concentration of glyoxaline compound is 0.1-1mol/L；
Preferably, manganese source and the molar ratio of glyoxaline compound are 1:5~1:9；
Preferably, the temperature of the sintering is 450-550 DEG C.
9. the application based on the described in any item manganese monoxide nano particles of claim 1-8, it is characterised in that: be used to prepare zinc
Ion battery anode.
10. the application based on the described in any item manganese monoxide nano particles of claim 1-8, it is characterised in that: be used to prepare
Zinc ion battery.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109950538A (en) * | 2019-04-15 | 2019-06-28 | 北京航空航天大学 | A kind of vanadium base anode material of Zinc ion battery |
| CN113929146A (en) * | 2021-09-23 | 2022-01-14 | 北京化工大学 | MnO/Mn with core-shell structure3O4Preparation and application of electrode material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015157142A1 (en) * | 2014-04-09 | 2015-10-15 | Retriev Technologies Incorporated | Recycle process for alkaline and carbon zinc batteries |
| CN105633373A (en) * | 2015-11-06 | 2016-06-01 | 北京化工大学 | Carbon-coated porous manganese monoxide composite material and preparation method and application thereof |
| CN106865618A (en) * | 2017-02-23 | 2017-06-20 | 广西大学 | One kind " peanut shape " Mn2O3The preparation method of/C particles |
| CN108539141A (en) * | 2018-03-06 | 2018-09-14 | 上海应用技术大学 | A kind of preparation method of the ternary layered positive electrode of sodium-ion battery |
-
2018
- 2018-11-29 CN CN201811447597.9A patent/CN109574078B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015157142A1 (en) * | 2014-04-09 | 2015-10-15 | Retriev Technologies Incorporated | Recycle process for alkaline and carbon zinc batteries |
| CN105633373A (en) * | 2015-11-06 | 2016-06-01 | 北京化工大学 | Carbon-coated porous manganese monoxide composite material and preparation method and application thereof |
| CN106865618A (en) * | 2017-02-23 | 2017-06-20 | 广西大学 | One kind " peanut shape " Mn2O3The preparation method of/C particles |
| CN108539141A (en) * | 2018-03-06 | 2018-09-14 | 上海应用技术大学 | A kind of preparation method of the ternary layered positive electrode of sodium-ion battery |
Non-Patent Citations (2)
| Title |
|---|
| LIV PETERS等: "Syntheses and structures of mononuclear manganese(II) complexes bearing bis(1-methylimidazol-2-yl)ketone ligands", 《INORGANICA CHIMICA ACTA》 * |
| S. MATERAZZI等: "Thermoanalytical studies of imidazole-substituted coordination compounds Mn(II)-complexes of bis(1-methylimidazol-2-yl)ketone", 《J THERM ANAL CALORIM》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109950538A (en) * | 2019-04-15 | 2019-06-28 | 北京航空航天大学 | A kind of vanadium base anode material of Zinc ion battery |
| CN113929146A (en) * | 2021-09-23 | 2022-01-14 | 北京化工大学 | MnO/Mn with core-shell structure3O4Preparation and application of electrode material |
| CN113929146B (en) * | 2021-09-23 | 2023-04-28 | 北京化工大学 | MnO/Mn with core-shell structure 3 O 4 Preparation and application of electrode material |
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