CN108511723A - A kind of mangaic acid cobalt/NC/S composite material and preparation methods and the application as lithium-sulfur rechargeable battery anode material - Google Patents
A kind of mangaic acid cobalt/NC/S composite material and preparation methods and the application as lithium-sulfur rechargeable battery anode material Download PDFInfo
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Abstract
The invention discloses a kind of CoMn2O4/ NC/S composite material and preparation methods and application as lithium-sulfur rechargeable battery anode.CoMn2O4/ NC/S composite materials are by mangaic acid cobalt (CoMn2O4) nano particle holdfast is combined with sulphur again in N doping graphitization porous carbon (NC), preparation method：By 67 calcination process of metal-organic framework materials ZIF, Co N C composites is obtained, then hydro-thermal reaction is carried out with manganese salt and permanganate, obtain CoMn2O4/ NC composite materials；It is further compound to get CoMn with sulphur2O4/ NC/S composite materials.The composite material can be carried out at the same time strong chemisorption and physical absorption to the polysulfide formed in lithium-sulfur rechargeable battery charge and discharge process, can effectively inhibit the loss by dissolution of polysulfide, reduce the generation of shuttle effect, improve the service life of lithium-sulfur rechargeable battery.The expensive toxic Co of Mn partial alternatives of the cheap low toxicity of this method is applied to lithium-sulfur rechargeable battery simultaneously, has important innovation and practice significance.
Description
Technical field
The present invention relates to a kind of lithium-sulfur cell materials, and in particular to a kind of CoMn2O4/ NC/S composite materials and its preparation side
Method, and by CoMn2O4Application of/NC/S the composite materials as lithium-sulfur rechargeable battery anode material, belongs to lithium-sulfur cell field.
Background technology
Recently as the rapid development of portable mobile apparatus and electric vehicle, two with higher energy density are developed
Primary cell system becomes very urgent.Currently, the specific energy density of commercial li-ion battery can reach 250Wh/kg, but due to
Positive electrode theoretical capacity is relatively low, and the further promotion of energy density is greatly limited.Therefore, new battery system is developed
It is imperative to unite.In new energy energy-storage system, since lithium-sulfur cell energy density is high, at low cost, resourceful, environmental-friendly
The features such as, it is considered to be one of most promising candidate's battery.However, its practical application nevertheless suffers from the obstruction of various factors.
First, element sulphur has poor electric conductivity, final reduzate Li2S2And Li2S is also electronic body；Secondly, it is filling
In discharge process, S8Molecule is a series of long-chain intermediate S by redoxn 2-(3≤n≤8), these intermediates are easy to molten
It in solution to organic bath, and then shuttles between positive and negative anodes, causes shuttle effect, lead to low cyclical stability and coulomb
Efficiency；Third, there are apparent volume expansion (about 80%) during lithiumation, whens charge and discharge, expands and shrinks repeatedly and can lead lithium
Cause the destruction of cell electrode structure.Therefore, the commercialized key problem of lithium-sulfur rechargeable battery is how to improve leading for active material
Electrical and stability, inhibits the shuttle effect of polysulfide.In view of the above-mentioned problems, the main solution of the prior art is：1)
Anode encapsulates sulphur, volume expansion caused by reduce sulphur and lithium sulfide in charge and discharge process with porous material；2) in anode
Conductive agent is added and sulphur progress is compound, solves the problems, such as sulphur poorly conductive；3) anode be added polar substances to polysulfide into
Row constraint, avoids the generation of shuttle effect；4) the selective diaphragm of certain pore size is prepared so that the polysulfide of long-chain can not be worn
It crosses diaphragm arrival cathode to be reacted with lithium metal, to solve the problems, such as shuttle effect；5) lithium nitrate is added in the electrolytic solution
Equal nitrate or other substances are passivated lithium metal surface, to slow down shuttle effect etc..
Invention content
For lithium sulfur battery anode material in the prior art, there are sulphur load capacity is low and the soluble loss of polysulfide
Technical problem, of the invention first purpose are to be that providing one kind can be pressed down by chemisorption and physical absorption synergistic effect
Polysulfide loss by dissolution processed reduces shuttle effect and occurs, and good conductivity, the high CoMn of stability2O4/ NC/S composite materials.
Second object of the present invention is to be to provide that a kind of step is simple, is easy to control, the preparation that cost of material is low
CoMn2O4The method of/NC/S composite materials.
Third object of the present invention is to be to provide CoMn2O4The application of/NC/S composite materials, as lithium sulphur two
Primary cell positive electrode application can improve the absorption to polysulfide, reduce the generation of shuttle effect, it is secondary to improve lithium sulphur
The service life of battery, and there is higher specific capacity and cyclical stability.
In order to achieve the above technical purposes, the present invention provides a kind of CoMn2O4The preparation method of/NC/S composite materials, should
Method includes the following steps：
1) cobalt salt and 2-methylimidazole are obtained into metal-organic framework materials ZIF-67 by liquid phase method；
2) the metal-organic framework materials ZIF-67 passes through calcination process, obtains Co-N-C composite materials；
3) Co-N-C composite materials are dispersed in manganese salt solution, after adding permanganate solution mixing, carry out hydro-thermal
Reaction, obtains CoMn2O4/ NC composite materials；
4) CoMn2O4/ NC composite materials and elemental sulfur after ball milling mixing, be heat-treated to get.
Technical scheme of the present invention using metal-organic framework materials (MOF) ZIF-67 as persursor material, ZIF-67 by
Cobalt ions is formed as metal center and 2-methylimidazole as ligand, has high-specific surface area, the skeleton structure of stabilization and hole
The feature that diameter is adjustable.And the product that ZIF-67 is generated after calcining is evenly distributed on the carbon matrix of N doping by Co nano-particles
It is constituted in material, and remains the distinctive skeleton structures of MOF, form a kind of metallic cobalt and nitrogen co-doped graphitization porous carbon
Expect (Co-N-C) there is high conductivity, the skeleton structure of stabilization and porous.The uniform abundant duct knots of Co-N-C
Structure can not only promote the transfer of electronics and ion in charge and discharge process, additionally it is possible to be effectively prevented the dissolving of polysulfide.
Cobalt simple substance in Co-N-C is reacted with manganese salt and permanganate, generates CoMn2O4/ NC composite materials, while it is porous to remain MOF
The structure of carbon.CoMn2O4Strong chemisorption can be carried out to the polysulfide formed in lithium-sulfur rechargeable battery charge and discharge process,
The graphitized carbon of N doping also can carry out physical absorption, the collective effect pole of this physics and chemisorption to polysulfide simultaneously
The earth improves absorption of the positive electrode to polysulfide, it is possible to reduce the generation of shuttle effect improves lithium-sulfur rechargeable battery
Service life.
The amount ratio of the substance of preferred scheme, cobalt salt and 2-methylimidazole is 1:2~32；More preferably it is 1:6~10.It is theoretical
The cobalt salt of upper ease of solubility is satisfied by the preparation requirement of metal-organic framework materials ZIF-67, the present invention with it is most common it is water-soluble compared with
Good cobalt nitrate is illustrated.The gold that cobalt salt can be stablized with 2-methylimidazole in preferred ratio range with generating structure
Belong to organic framework material ZIF-67 crystal.
Preferred scheme, the calcination process process are：It is placed under protective atmosphere, under 600~1000 DEG C of high temperature, heat preservation
1~5h.Protective atmosphere is nitrogen, or other inert gases, here preferentially using cheap nitrogen as protective atmosphere.
More preferably scheme, the calcination process process are：It is placed under nitrogen atmosphere, under 700~900 DEG C of high temperature, keeps the temperature 2~4h.
Under preferred roasting condition, metal-organic framework materials ZIF-67 can substantially keep its original structure pattern, and cobalt from
Son is reduced into cobalt nanometer particle, and 2-methylimidazole is converted to nitrogen-doped carbon.
Preferred scheme, the amount ratio of cobalt and the substance of manganese in manganese in manganese salt solution and permanganate in Co-N-C composite materials
It is 1:150~250:20~50.More preferably scheme, in Co-N-C composite materials cobalt in manganese in manganese salt solution and permanganate
The amount ratio of the substance of manganese is 1:180~220:30~40.
Preferred scheme, the hydrothermal reaction process are：At a temperature of 130~180 DEG C, hydro-thermal reaction 6~for 24 hours.It is more excellent
The scheme of choosing, hydrothermal reaction process are：At a temperature of 150~170 DEG C, 10~14h of hydro-thermal reaction.In hydrothermal reaction process,
With manganese salt and permanganate redox reaction occurs for cobalt simple substance, generates CoMn2O4, and deposit and be supported on NC materials.
Preferred scheme, the CoMn2O4The mass ratio of/NC composite materials and elemental sulfur is 1:1~6, it is more preferably 1:2
~4.
Preferred scheme, the ball milling mixing process are：At ambient temperature, with 100~500r/min rotating speeds, ball milling 1
~10h.More preferably scheme, the ball milling mixing process are：At ambient temperature, with 200~400r/min rotating speeds, ball milling 2
~5h.It can make CoMn by ball milling2O4/ NC composite materials are sufficiently mixed the load for being uniformly conducive to sulphur with elemental sulfur.
Preferred scheme, the heat treatment process are：In nitrogen atmosphere, first it is warming up at a temperature of 145~165 DEG C
8~16h is managed, then is warming up to 190~210 DEG C of 20~40min of processing.Most preferred scheme, heat treatment process are：In nitrogen atmosphere
In, 12h is handled at a temperature of being first warming up to 155 DEG C, then be warming up to 200 DEG C of processing 300min.By heat treatment process, keep sulphur equal
It is even to be supported on CoMn2O4In the pore structure of/NC composite materials.
Preferred scheme, manganese salt are water-soluble manganese salt, such as manganese sulfate.
Preferred scheme, permanganate are high water solubility manganate, such as potassium permanganate.
The present invention also provides a kind of CoMn2O4/ NC/S composite materials, are obtained by above-mentioned preparation method.CoMn2O4/
NC/S composite materials are by CoMn2O4Nano particle holdfast is consolidated sulphur on N doping graphitization porous carbon (NC) and is constituted again.
The present invention also provides a kind of CoMn2O4The application of/NC/S composite materials, as lithium-sulfur rechargeable battery anode
Material application.
The CoMn of the present invention2O4/ NC/S composite materials are applied to the preparation of lithium-sulfur rechargeable battery anode as positive electrode：
By CoMn2O4/ NC/S composite materials and conductive agent conductive black, binder Kynoar (PVDF) and Solvents N-methyl pyrroles
Alkanone (NMP) is mixed and made into slurry, is coated on aluminium foil, after drying to obtain the final product.
The CoMn of the present invention2O4The preparation method of/NC/S composite materials, includes the following steps：
1) cobalt nitrate and 2-methylimidazole are dissolved in respectively in organic alcoholic solution, are stood after being sufficiently mixed, through centrifugal drying
Obtain metal-organic framework materials (MOF) ZIF-67 crystal；
2) by ZIF-67 crystal high-temperature process under an inert atmosphere, Co-N-C composite materials are obtained；
3) Co-N-C is distributed in manganese sulfate solution, liquor potassic permanganate is then added, be sufficiently mixed laggard
Row hydro-thermal reaction obtains CoMn after washed, dry2O4/ NC composite materials；
4) by the CoMn2O4/ NC composite materials and elemental sulfur are through ball milling mixing, then under an inert atmosphere at high temperature
Reason is to get CoMn2O4/ NC/S composite materials.
The present invention provides a kind of CoMn for lithium-sulfur rechargeable battery anode2O4/ NC/S composite material and preparation methods,
Compared with prior art, technical scheme of the present invention advantage is：
1) present invention is expensive using cheap and less toxic manganese partial alternative and the cobalt that is more toxic prepares lithium
Sulfur rechargeable battery anode material has important innovation and practice significance.
2) CoMn of the invention2O4/ NC/S composite materials have a large amount of micropore, meso-hole structure, and stable structure, can
When efficiently solving lithium-sulfur rechargeable battery charge and discharge the problem of volume expansion.
3) CoMn of the invention2O4CoMn in/NC/S composite materials2O4It can be to the polysulfide that is formed in charge and discharge process
Strong chemisorption is carried out, while N doping graphitized carbon also can carry out physical absorption, this physics and change to polysulfide
The collective effect for learning absorption greatly improves absorption of the positive electrode to polysulfide, reduces the generation of shuttle effect, improves
Service life of lithium-sulfur rechargeable battery.
4) CoMn of the invention2O4/ NC/S composite materials have higher specific capacity as lithium-sulfur rechargeable battery anode material
And cyclical stability, such as at 0.1C, the first discharge specific capacity of lithium-sulfur rechargeable battery is up to 1329.7mAh/g.
5) CoMn of the invention2O4/ NC/S composite material preparation process is simple, and cost of material is low, is conducive to extensive life
Production.
Description of the drawings
【Fig. 1】For the XRD and thermal multigraph of material prepared in embodiment 1.Wherein, a is the powder X-ray of prepared ZIF-67
X ray diffraction (XRD) spectrogram shows that prepared ZIF-67 has high-crystallinity, with document (Energy Environ.Sci.,
2016,9,199–2004；Electrochim.Acta, 2016,218,243-251) it is consistent；B is ZIF-67 by 800 DEG C of calcinings
The XRD spectra of Co-N-C afterwards.PDF#15-0806 is the standard x RD spectrograms of simple substance Co, shows the cobalt ions in ZIF-67 skeletons
It is reduced to form simple substance cobalt.In addition, diffraction maximum small and wide near 26.1 ° is the characteristic peak of graphitic carbon, show Co-N-C
Successful preparation；C is CoMn2O4The XRD spectra of/NC.PDF#01-112 is CoMn2O4Standard x RD spectrograms, positioned at 26.1 °
Diffraction maximum is the characteristic peak of graphitic carbon, shows CoMn2O4The successful preparation of/NC；D is CoMn2O4The heat of/NC/S and Co-N-C/S
Multigraph.Wherein, the weight loss in 150~300 DEG C of sections is mainly due to the distillation of sulphur, shows CoMn2O4/ NC/S and Co-N-C/
Sulfur content in S composite materials is respectively 69.1% and 63.3%.
【Fig. 2】For CoMn prepared in embodiment 12O4The XPS of/NC composite materials schemes.It is CoMn to scheme a2O4/ NC is compound
The XPS of material is composed entirely；In the C 1s spectrograms (figure b) of fitting, it is located at the main peak at 284.5eV and corresponds to sp2Hydridization carbon,
Peak at 286.1eV and 287.1eV corresponds respectively to C=N keys and C-N keys.The above results definitely confirm the shape of C-N keys
At；High-resolution N 1s XPS spectrum figures further demonstrate the presence (figure c) of nitrogen species in composite material.In N 1s spectrograms,
Three characteristic peaks of energy are combined to correspond respectively to pyridine nitrogen, pyrroles's nitrogen and graphite nitrogen in 398.2eV, 99.7eV and 401.3eV.
In O 1s spectrograms (figure d), the peak at 529.7eV, 530.0eV and 530.1eV confirms Co-O, Mn-O and O-respectively
The presence of Mn-O；Peak in Co 2p spectrograms at (figure e) 780.2eV further demonstrates the presence of Co-O；And in Mn 2p3/2
Peak in spectrogram at (figure f) 641.0eV and 641.6eV further demonstrates the presence of Mn-O and O-Mn-O respectively.
【Fig. 3】For SEM and the TEM figure of material prepared in embodiment 1.Wherein, a and e be respectively ZIF-67 SEM and
TEM schemes, and shows that prepared ZIF-67 particles are in uniform granatohedron shape, has smooth surface, average particle size
About 800nm；The SEM and TEM that b and f is Co-N-C scheme.In a nitrogen atmosphere after 800 DEG C of carbonizations, gained Co-N-C composite woods
Material inherits the similarly sized of parent ZIF-67 and whole polyhedral pattern, other than there is slight collapse on surface, Co nanometers
Particle is evenly distributed in the matrix of carbon；C and g is respectively CoMn2O4The SEM and TEM of/NC composite materials scheme, and show CoMn2O4/
NC composite materials substantially on maintain the shape of Co-N-C, CoMn2O4The grain size of nano particle is relative to the Co nanometers in Co-N-C
Particle has apparent increase；D and h is respectively CoMn2O4The SEM and TEM of/NC/S schemes, and shows to penetrate into the load of sulphur,
CoMn2O4/ NC/S composite materials maintain dodecahedral shape.
【Fig. 4】Electrochemistry for material prepared in embodiment 1 as the assembled battery of lithium-sulfur rechargeable battery anode material institute
The performance test results.Wherein, a CoMn2O4The charging/discharging voltage curve graph of/NC/S combination electrodes under different multiplying；B is
CoMn2O4The high rate performance and coulombic efficiency figure of/NC/S and Co-N-C/S electrodes；C is CoMn2O4/ NC/S electrodes are under 1C multiplying powers
The charging/discharging voltage curve graph of difference cycle；D is CoMn2O4Cycle performance and coulomb of/NC/S the and Co-N-C/S electrodes in 1C are imitated
Rate figure.
Specific implementation mode
The content of present invention is more fully described with embodiment below, but is not intended to limit the protection model of the claims in the present invention
It encloses.
Embodiment 1
CoMn2O4The preparation of/NC/S composite materials：
(1) 2-methylimidazole of the cabaltous nitrate hexahydrate of 1.455g and 3.28g are dissolved in the methanol of 100mL respectively.So
Afterwards, the clear solution of 2-methylimidazole is poured into cobalt nitrate solution rapidly with vigorous stirring.After being sufficiently mixed, solution is in room
Temperature is lower to stand one day.By obtained purple precipitation absolute ethyl alcohol centrifuge washing 3 times, dry 12h, obtains ZIF-67 at 70 DEG C
Crystal.
(2) the ZIF-67 crystal of synthesis is calcined into 3h under stream of nitrogen gas at 800 DEG C, the rate of heat addition is 5 DEG C/min, is obtained
To Co-N-C composite materials.
(3) Co-N-C the and 93.2mg manganese sulfates of 0.2g are disperseed and are dissolved in 35mL deionized waters, simultaneously will
29.2mg potassium permanganate is dissolved in 35mL deionized waters, after the two ultrasound 30min is sufficiently mixed, be transferred in reaction kettle in
Hydro-thermal reaction 12h at 160 DEG C.It is washed 3 times, after filtering with water and ethyl alcohol, dry 12h, obtains CoMn at 70 DEG C2O4/ NC is compound
Material.
(4) by the CoMn of 0.15g2O4/ NC composite materials and 0.35g elemental sulfur ball milling 3h, prior to 155 in nitrogen atmosphere
12h is handled at DEG C, then heats to 200 DEG C of processing 30min.After natural cooling, CoMn is obtained2O4/ NC/S composite materials.
The preparation and performance test of electrode：
By the CoMn prepared by embodiment 12O4/ NC/S composite materials, conductive black and PVDF in mass ratio 70:20:10
It is mixed and stirred into uniform slurry in NMP, then black paste is coated on aluminium foil, and is dried in vacuum overnight at 60 DEG C
To obtain cathode.Metal lithium sheet is anode, and CELGARD 2400 is diaphragm, 3- dioxolanes/glycol dimethyl ether of 1mol/L
Base two (trifluoromethane sulfonic acid) imine lithium (volume ratio 1:1) it is electrolyte, the LiNO of 1mol/L3For additive, full of nitrogen
Glove box in be assembled into button cell, using Land battery test systems to battery carry out electrochemical property test.Fig. 4 (a)
For CoMn2O4The electric discharge and charging voltage curve graph that/NC/S composite materials recycle for the first time under different multiplying, even if 2C's
Also identical electric discharge and charging platform pattern are shown under high magnification.Discharge curve shows the typical Double tabletop row of sulphur cathode
To correspond to and forming long-chain polysulphides and the formation short chain Li at 2.04V at 2.30V2S2And Li2S；CoMn2O4/ NC/S and
Shown in the chemical property that Co-N-C/S composite materials recycle under different multiplying such as Fig. 4 (b).Under the multiplying power of 0.1C,
CoMn2O4/ NC/S can provide the initial discharge capacity of 1329.7mAh/g and intimate 100% coulombic efficiency.0.2,0.5,1
The high reversible capacity that 1070.5,891.7,794.8 and 650.3mAh/g is shown with the further cycle under 2C multiplying powers, show compared with
Good electrode reaction dynamics.When multiplying power reverts again to 0.5,0.2 and 0.1C, 830.4,896.2 and are also can reach
The reversible capacity of 905.6mAh/g shows that electrode material is with good stability after high rate cyclic.In addition, different
Under multiplying power, electric discharge and charging capacity are stablized, and coulombic efficiency nearly reaches 100%, it was demonstrated that the shuttle effect of polysulfide obtains
Preferable control；Fig. 4 (c) is CoMn when being recycled at 1,10,50,100,300 and 500 time2O4The charging/discharging voltage of/NC/S is bent
Line chart；That Fig. 4 (d) is disclosed is the CoMn when multiplying power is 1C2O4The cycle performance of/NC/S and Co-N-C/S composite materials.1C's
Under multiplying power, the initial discharge capacity of the material is 1045.4mAh/g, in addition to the Capacity fading of first time comparatively fast other than, can
Keep relatively stable cycle performance.
Embodiment 2
CoMn2O4The preparation of/NC/S composite materials：
(1) 2-methylimidazole of the cabaltous nitrate hexahydrate of 1.455g and 1.64g are dissolved in the methanol of 70mL respectively.So
Afterwards, the clear solution of 2-methylimidazole is poured into cobalt nitrate solution rapidly with vigorous stirring.After being sufficiently mixed, solution is in room
Temperature is lower to stand one day.The purple precipitation absolute ethyl alcohol centrifuge washing 3 times, 70 DEG C of dry 12h that will be obtained obtains ZIF-67 crystalline substances
Body.
(2) the ZIF-67 crystal of synthesis is calcined to 5h under stream of nitrogen gas in 700 DEG C, the rate of heat addition is 3 DEG C/min, is obtained
Co-N-C composite materials.
(3) Co-N-C the and 86.2mg manganese sulfates of 0.15g are disperseed and are dissolved in 35mL deionized waters, simultaneously will
43.2mg potassium permanganate is dissolved in 35mL deionized waters, and after the two ultrasound 30min is sufficiently mixed, mixture is transferred to instead
Answer in kettle the hydro-thermal reaction 10h at 180 DEG C.It is washed 3 times, after filtering with water and ethyl alcohol, dry 12h, obtains at 70 DEG C
CoMn2O4/ NC composite materials.
(4) by the CoMn of 0.12g2O4/ NC composite materials and 0.34g elemental sulfur ball milling 2h, prior to 180 in nitrogen atmosphere
6h is handled at DEG C, then heats to 200 DEG C of processing 15min.After natural cooling, CoMn is obtained2O4/ NC/S composite materials.
The preparation and performance test of electrode are the same as embodiment 1.
Prepared CoMn2O4/ NC/S composite materials under the multiplying power of 0.1C, hold by the electric discharge that can provide 1285.9mAh/g
Measure the coulombic efficiency with intimate 100%.Under the multiplying power of 1C, the initial discharge capacity of the material is 1035.2mAh/g.
Embodiment 3
CoMn2O4The preparation of/NC/S composite materials：
(1) 2-methylimidazole of the cabaltous nitrate hexahydrate of 1.455g and 6.56g are dissolved in the methanol of 150mL respectively.So
Afterwards, the clear solution of 2-methylimidazole is poured into cobalt nitrate solution rapidly with vigorous stirring.After being sufficiently mixed, solution is in room
Temperature is lower to stand one day.By obtained purple precipitation absolute ethyl alcohol centrifuge washing 3 times, dry 12h, obtains ZIF-67 at 70 DEG C
Crystal.
(2) the ZIF-67 crystal of synthesis is calcined to 2h under stream of nitrogen gas in 900 DEG C, the rate of heat addition is 5 DEG C/min, is obtained
Co-N-C composite materials.
(3) Co-N-C the and 46.6mg manganese sulfates of 0.25g are disperseed and are dissolved in 35mL deionized waters, simultaneously will
14.6mg potassium permanganate is dissolved in 35mL deionized waters, and after the two ultrasound 30min is sufficiently mixed, mixture is transferred to instead
It answers in kettle in 150 DEG C of hydro-thermal reactions for 24 hours.It is washed 3 times, after filtering with water and ethyl alcohol, dry 12h, obtains CoMn at 70 DEG C2O4/
NC composite materials.
(4) by the CoMn of 0.18g2O4/ NC composite materials and 0.25g elemental sulfur ball milling 3h, prior to 170 in nitrogen atmosphere
8h is handled at DEG C, then heats to 200 DEG C of processing 20min.After natural cooling, CoMn is obtained2O4/ NC/S composite materials.
The preparation and performance test of electrode are the same as embodiment 1.
Prepared CoMn2O4/ NC/S composite materials under the multiplying power of 0.1C, hold by the electric discharge that can provide 1296.5mAh/g
Measure the coulombic efficiency with intimate 100%.Under the multiplying power of 1C, the initial discharge capacity of the material is 1013.8mAh/g.
Embodiment 4
CoMn2O4The preparation of/NC/S composite materials：
(1) 2-methylimidazole of the cabaltous nitrate hexahydrate of 2.142g and 25.24g are dissolved in the methanol of 300mL respectively.So
Afterwards, the clear solution of 2-methylimidazole is poured into cobalt nitrate solution rapidly with vigorous stirring.After being sufficiently mixed, solution is in room
Temperature is lower to stand one day.By obtained purple precipitation absolute ethyl alcohol centrifuge washing 3 times, dry 12h, obtains ZIF-67 at 70 DEG C
Crystal.
(2) the ZIF-67 crystal of synthesis is calcined to 4h under stream of nitrogen gas in 850 DEG C, the rate of heat addition is 2 DEG C/min, is obtained
Co-N-C composite materials.
(3) Co-N-C the and 280mg manganese sulfates of 0.5g are disperseed and are dissolved in 35mL deionized waters, while by 88mg high
Potassium manganate is dissolved in 75mL deionized waters, after the two ultrasound 30min is sufficiently mixed, is transferred in reaction kettle in 180 DEG C of water
Thermal response 16h.It is washed 3 times, after filtering with water and ethyl alcohol, dry 12h, obtains CoMn at 70 DEG C2O4/ NC composite materials.
(4) by the CoMn of 0.3g2O4/ NC composite materials and 0.7g elemental sulfur ball milling 5h, prior to 165 DEG C in nitrogen atmosphere
Lower processing 10h then heats to 200 DEG C of processing 10min.After natural cooling, CoMn is obtained2O4/ NC/S composite materials.
The preparation and performance test of electrode are the same as embodiment 1.
Prepared CoMn2O4/ NC/S composite materials under the multiplying power of 0.1C, hold by the electric discharge that can provide 1304.3mAh/g
Measure the coulombic efficiency with intimate 100%.Under the multiplying power of 1C, the initial discharge capacity of the material is 1019.6mAh/g.
Comparative example 1
The preparation of Co-N-C/S composite materials：
Co-N-C composite materials are prepared as described in Example 1.By the Co-N-C composite materials of 0.3g and 0.7g elemental sulfurs
Ball milling 3h, in nitrogen atmosphere prior to 155 DEG C at handle 12h, then heat to 200 DEG C processing 30min.After natural cooling, obtain
To Co-N-C/S composite materials.
The preparation and performance test of electrode are the same as embodiment 1.
Prepared Co-N-C/S composite materials can provide the discharge capacity of 1085.9mAh/g under the multiplying power of 0.1C
With intimate 100% coulombic efficiency.Under the multiplying power of 1C, the initial discharge capacity of the material is 785.2mAh/g.
Claims (10)
1. a kind of CoMn2O4The preparation method of/NC/S composite materials, it is characterised in that：
1) cobalt salt and 2-methylimidazole are obtained into metal-organic framework materials ZIF-67 by liquid phase method；
2) the metal-organic framework materials ZIF-67 passes through calcination process, obtains Co-N-C composite materials；
3) Co-N-C composite materials are dispersed in manganese salt solution, after adding permanganate solution mixing, carry out hydro-thermal reaction,
Obtain CoMn2O4/ NC composite materials；
4) CoMn2O4/ NC composite materials and elemental sulfur after ball milling mixing, be heat-treated to get.
2. a kind of CoMn according to claim 12O4The preparation method of/NC/S composite materials, it is characterised in that：Cobalt salt with
The amount ratio of the substance of 2-methylimidazole is 1:2~32.
3. a kind of CoMn according to claim 12O4The preparation method of/NC/S composite materials, it is characterised in that：The roasting
Burning processing procedure is：It is placed under protective atmosphere, under 600~1000 DEG C of high temperature, keeps the temperature 1~5h.
4. a kind of CoMn according to claim 12O4The preparation method of/NC/S composite materials, it is characterised in that：Co-N-C
The amount ratio of cobalt and the substance of manganese in manganese in manganese salt solution and permanganate is 1 in composite material:150~250:20~50.
5. a kind of CoMn according to claim 1 or 42O4The preparation method of/NC/S composite materials, it is characterised in that：It is described
Hydrothermal reaction process is：At a temperature of 130~180 DEG C, hydro-thermal reaction 6~for 24 hours.
6. a kind of CoMn according to claim 12O4The preparation method of/NC/S composite materials, it is characterised in that：It is described
CoMn2O4The mass ratio of/NC composite materials and elemental sulfur is 1:1~6.
7. a kind of CoMn according to claim 1 or 62O4The preparation method of/NC/S composite materials, it is characterised in that：It is described
Ball milling mixing process is：At ambient temperature, with 100~500r/min rotating speeds, 1~10h of ball milling.
8. a kind of CoMn according to claim 12O4The preparation method of/NC/S composite materials, it is characterised in that：The heat
Processing procedure is：In nitrogen atmosphere, 8~16h is handled at a temperature of being first warming up to 145~165 DEG C, then be warming up to 190~210
DEG C processing 20~40min.
9. a kind of CoMn2O4/ NC/S composite materials, it is characterised in that：It is obtained by any one of claim 1~8 preparation method.
10. a kind of CoMn described in claim 92O4The application of/NC/S composite materials, it is characterised in that：As the secondary electricity of lithium sulphur
Pond positive electrode application.
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