CN107017400A - The preparation method and applications of manganese carbonate/mangano-manganic oxide/graphene trielement composite material - Google Patents
The preparation method and applications of manganese carbonate/mangano-manganic oxide/graphene trielement composite material Download PDFInfo
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Abstract
The preparation method and applications of manganese carbonate/mangano-manganic oxide/graphene trielement composite material, the present invention relates to a kind of preparation method of lithium ion battery negative material, it will solve the long preparation period of existing used as negative electrode of Li-ion battery manganese carbonate/graphene composite material, the problem of chemical property is relatively low.Preparation method:First, graphite is put into H2SO4In solution, KMnO is added4, temperature, which is increased to after 85~98 DEG C, adds deionized water and H2O2, obtain Mn/ graphite oxide solutions;2nd, it is ultrasonically treated;3rd, sodium carbonate liquor, the pH to 9~11 of regulation system are added;4th, heating water bath, is collected by filtration precipitation, manganese carbonate/mangano-manganic oxide/graphene trielement composite material is obtained after cleaning, drying.Invention will prepare manganese source of the manganese in potassium permanganate used in graphite oxide as follow-up composite, improve raw material availability, shortens preparation time, cycle performance and specific capacity are enhanced as lithium ion battery negative material.
Description
Technical field
Manganese carbonate/mangano-manganic oxide/graphene trielement composite material and conduct are prepared the present invention relates to a kind of green method
The application of lithium ion battery negative material.
Background technology
The problem of a series of environmental pollutions triggered due to the use of traditional fuel current and energy scarcity, receives people
Very big concern.In order to fundamentally solve relevant issues, the exploitation novel environment friendly energy turns into the focus of attention.Lithium ion battery
As a kind of device that chemical energy is converted into electric energy, the problems such as effectively can alleviating environmental pollution, and obtain opening energetically
Hair and research.But the currently commercially lithium ion battery negative material used, graphite, its low specific capacity (372mAh g-1)
It significantly limit practical application, it is impossible to meet the fast-developing demand such as portable set and electric automobile.
At present, transition group carbonate, particularly manganese carbonate, due to its higher specific capacity (1000+mAh g-1, it is current
3 times of commercial Li-ion battery graphite cathode material specific capacity) and attract attention.But, there is also electric conductivity for manganese carbonate
Poor the problems such as, cause cycle performance poor.By being combined with this material with good conductivity of graphene, can effectively it change
The combination property of kind transition group carbonate.The method for mainly preparing composite at present is hydro-thermal method or solvent-thermal method, main step
Suddenly it is first to prepare graphite oxide, then adds manganese salt and corresponding precipitating reagent, by hydro-thermal or solvent thermal reaction, then by washing
Wash and dry and obtain manganese carbonate/graphene composite material.But, current technique during graphite oxide is prepared, is passed through
After oxidation reaction, there is more Mn in its solution2+, and strong acid etc., the waste of raw material and the pollution of environment are caused,
Simultaneously during subsequently manganese carbonate/graphene composite material is prepared, manganese salt and organic solvent etc. are further added, can also be produced
Raw corresponding waste and pollution, and entirely manufacturing cycle is extended.And composite is prepared for hydro-thermal and solvent-thermal method, by
In being limited by device and experiment condition is limited, it is difficult to it is real realize it is extensive prepare so that can not carry out it is actual should
With.
The content of the invention
The invention aims to solve the preparation week of existing used as negative electrode of Li-ion battery manganese carbonate/graphene composite material
Phase is long, the problem of chemical property is relatively low, and provides a kind of green method manganese carbonate/mangano-manganic oxide/graphene tri compound material
The preparation method and applications of material.
The preparation method of manganese carbonate/mangano-manganic oxide/graphene trielement composite material of the present invention follows these steps to realize:
The first, 1~10g graphite be put into 23~230ml H2SO4In solution, 20~60min is stirred at 0~5 DEG C, then
Add 4~40g KMnO4, 2~3h of stirring at 0~5 DEG C is maintained at, temperature is then increased to 30~45 DEG C, 2 are kept stirring for
~3h, is further increased to 85~98 DEG C by temperature, continues to stir 10~30min, add 150~1500ml deionized waters and
10~100ml H2O2, cool down and obtain Mn/ graphite oxide solutions;
2nd, the Mn/ graphite oxide solutions for obtaining step one handle 2~3h under ultrasound, obtain Mn/ graphene oxides molten
Liquid;
3rd, during stirring, sodium carbonate liquor (slow) is added dropwise in Mn/ graphene oxide solutions, body is adjusted
The pH of system obtains manganese carbonate/mangano-manganic oxide/graphene solution to 9~11;
4th, manganese carbonate/mangano-manganic oxide/graphene solution that step 3 is obtained is placed in 90~98 DEG C of water-bath, protected
2~3h of stirring is held, is then collected by filtration and is precipitated and cleaned with deionized water, the oxidation of manganese carbonate/tetra- is obtained after freeze-drying
Three manganese/graphene trielement composite material.
The present invention bears manganese carbonate/mangano-manganic oxide/graphene trielement composite material as the battery in lithium ion battery
Pole material.
Manganese carbonate/mangano-manganic oxide/graphene composite material that the present invention is prepared, shows that its is pure by XRD analysis
Degree is high, does not contain other impurities product, and by controlling manganese carbonate and four oxygen in the pH value of final solution, regulation composite
The pH value for changing system in the relative amount of three manganese, i.e. step 3 is bigger, and the content of mangano-manganic oxide is higher in composite.Carbonic acid
The TEM photos of manganese/mangano-manganic oxide/graphene composite material show that it is loose porous three-dimensional grapheme structure, bending
Graphene nanometer sheet interconnects.Manganese carbonate micron ball is made up of many manganese carbonate nano particles, and mangano-manganic oxide is received
Rice grain is evenly scattered in around manganese carbonate microballoon and internal, while all nano particles are all tightly in situ with graphene
It is combined with each other.This structure is favorably improved the electric conductivity of material, simultaneous buffering Volume Changes caused by discharge and recharge, so that
Greatly improve the cycle performance of negative material.Manganese carbonate/mangano-manganic oxide/graphene the negative material is tested in 1000mA
g-1Current density under, circulate 800 times, specific capacity is maintained at 532mAh g-1, 100mA g-1It is lower to circulate 200 times, keep
988mAh g-1, and better than single manganese carbonate/graphene composite material (100mA g-1, 200 circulations, 426mAh g-1)。
The present invention prepares manganese carbonate/mangano-manganic oxide/graphene three using the method for step green co-precipitation first
First composite, greatly improves the utilization rate of raw material, and shortens process cycle, reduces production cost, reduces
Environmental pollution.And manganese carbonate/mangano-manganic oxide/graphene trielement composite material, during as lithium-ion negative pole, improve conduction
Property, its cycle performance is greatly improved, with series of advantages such as specific area, height ratio capacity and long circulation lifes, it is adaptable to
In various portable electric appts and electric automobile.Against existing technologies, present invention process is reasonable, environmental protection, easy to operate,
Excellent performance, is a kind of preferable lithium ion battery negative material.
Brief description of the drawings
Fig. 1 is the XRD for manganese carbonate/mangano-manganic oxide/graphene trielement composite material that embodiment one is obtained, wherein A
Represent Mn3O4, B represents MnCO3;
Fig. 2 is the TEM figures for manganese carbonate/mangano-manganic oxide/graphene trielement composite material that embodiment one is obtained;
Fig. 3 is Mn in manganese carbonate/mangano-manganic oxide/graphene trielement composite material that embodiment one is obtained3O4HRTEM
Figure;
Fig. 4 is Mn in manganese carbonate/mangano-manganic oxide/graphene trielement composite material that embodiment one is obtained3O4EDS figure;
Fig. 5 is MnCO in manganese carbonate/mangano-manganic oxide/graphene trielement composite material that embodiment one is obtained3HRTEM
Figure;
Fig. 6 is MnCO in manganese carbonate/mangano-manganic oxide/graphene trielement composite material that embodiment one is obtained3EDS
Figure;
Fig. 7 is that the chemical property for manganese carbonate/mangano-manganic oxide/graphene trielement composite material that embodiment one is obtained is surveyed
Attempt;
Fig. 8 is the specific capacity test chart for two kinds of composites that embodiment one and comparative example are obtained;
Fig. 9 is the impedance plot for two kinds of composites that embodiment one and comparative example are obtained, wherein ● represent
MnCO3/Mn3O4/ RGO trielement composite materials, represents MnCO3/ RGO composites.
Embodiment
Embodiment one:The preparation side of present embodiment manganese carbonate/mangano-manganic oxide/graphene trielement composite material
Method follows these steps to implement:
The first, 1~10g graphite be put into 23~230ml H2SO4In solution, 20~60min is stirred at 0~5 DEG C, then
Add 4~40g KMnO4, 2~3h of stirring at 0~5 DEG C is maintained at, temperature is then increased to 30~45 DEG C, 2 are kept stirring for
~3h, is further increased to 85~98 DEG C by temperature, continues to stir 10~30min, add 150~1500ml deionized waters and
10~100ml H2O2, cool down and obtain Mn/ graphite oxide solutions;
2nd, the Mn/ graphite oxide solutions for obtaining step one handle 2~3h under ultrasound, obtain Mn/ graphene oxides molten
Liquid;
3rd, during stirring, sodium carbonate liquor (slow) is added dropwise in Mn/ graphene oxide solutions, body is adjusted
The pH of system obtains manganese carbonate/mangano-manganic oxide/graphene solution to 9~11;
4th, manganese carbonate/mangano-manganic oxide/graphene solution that step 3 is obtained is placed in 90~98 DEG C of water-bath, protected
2~3h of stirring is held, is then collected by filtration and is precipitated and cleaned with deionized water, the oxidation of manganese carbonate/tetra- is obtained after freeze-drying
Three manganese/graphene trielement composite material.
Sodium carbonate liquor is slowly dropped in solution in present embodiment step 3, the pH value of regulation system passes through pH
Value is different, makes the content of two kinds of manganese salts in the product that finally gives different.
It is typically all first to prepare graphite oxide, raw material bag during existing preparation manganese systems/graphene composite material
Graphite is included, sulfuric acid, potassium permanganate, hydrogen peroxide, obtained product is washed through persalt, then will wherein with substantial amounts of deionized water
Accessory substance (H+, Mn2+,SO4 2-) etc. washing, dialysis, be then dried to obtain graphite oxide, then graphite oxide is added to the water
Or ultrasonic disperse is carried out in solvent, then rejoin new manganese source, then by hydro-thermal method or solvent-thermal method prepare manganese systems/
Graphene composite material.And the present invention is to regard the manganese prepared in potassium permanganate used in graphite oxide as follow-up composite
Manganese source, improve the utilization rate of raw material, reduce the dry step of washing, cost and time have been saved, while in preparation
Process, because the dropwise addition of aqueous slkali can neutralize the acid in solution, so also playing the effect for reducing environmental pollution.
Embodiment two:H unlike present embodiment and embodiment one described in step one2SO4It is molten
The mass concentration of liquid is 98%.Other steps and parameter are identical with embodiment one.
Embodiment three:Step one unlike present embodiment and embodiment one or two puts 1g graphite
The mass concentration for entering 23ml is 98% H2SO4In solution, 20~60min is stirred at 0~5 DEG C, 5g KMnO is then added4。
Other steps and parameter are identical with embodiment one or two.
Embodiment four:Step one unlike one of present embodiment and embodiment one to three is by temperature
45 DEG C are increased to, 2h is kept stirring for, temperature is further increased to 95 DEG C, continues to stir 30min, adds 150ml deionizations
Water and 15ml H2O2.Other steps and parameter are identical with one of embodiment one to three.
Embodiment five:Step 2 is with 80 unlike one of present embodiment and embodiment one to four
2~3h is handled under~100W power ultrasonic.Other steps and parameter are identical with one of embodiment one to four.
Embodiment six:Carbonic acid in step 3 unlike one of present embodiment and embodiment one to five
The concentration of sodium solution is 0.05~0.2mol/L.Other steps and parameter are identical with one of embodiment one to five.
Embodiment seven:Step 3 regulation body unlike one of present embodiment and embodiment one to six
The pH of system to 10~11.Other steps and parameter are identical with one of embodiment one to six.
Embodiment eight:The pH of step 3 regulation system unlike present embodiment and embodiment seven is extremely
11.Other steps and parameter are identical with embodiment seven.
Embodiment nine:Freezed in step 4 unlike one of present embodiment and embodiment one to eight
Drying is dried in vacuo at -70 DEG C.Other steps and parameter are identical with one of embodiment one to eight.
Embodiment ten:Step 4 unlike one of present embodiment and embodiment one to nine is by carbonic acid
Manganese/mangano-manganic oxide/graphene solution is placed in 95 DEG C of water-bath, is kept stirring for 2h.Other steps and parameter and specific implementation
One of mode one to nine is identical.
Embodiment one:The preparation method of the present embodiment manganese carbonate/mangano-manganic oxide/graphene trielement composite material is by following
Step is implemented:
The first, 1g graphite be put into 23ml H2SO4In solution (mass concentration is 98%), 60min is stirred at 0 DEG C, then
Add 5g KMnO4, it is maintained at 0 DEG C and stirs 2h, temperature is then increased to 45 DEG C, be kept stirring for 2h, further by temperature
98 DEG C are increased to, continues to stir 30min, adds 150ml deionized waters and 15ml H2O2, it is molten that cooling obtains Mn/ graphite oxides
Liquid;
2nd, the Mn/ graphite oxide solutions for obtaining step one handle 2h under ultrasound, obtain Mn/ graphene oxide solutions;
3rd, during stirring, concentration is slowly dropped into Mn/ graphene oxides for 0.1mol/L sodium carbonate liquor
In solution, the pH=11 of regulation system obtains manganese carbonate/mangano-manganic oxide/graphene solution;
4th, manganese carbonate/mangano-manganic oxide/graphene solution that step 3 is obtained is placed in 95 DEG C of water-bath, keeps stirring
2h is mixed, is then collected by filtration and precipitates and cleaned with deionized water, manganese carbonate/mangano-manganic oxide/stone is obtained after freeze-drying
Black alkene (MnCO3/Mn3O4/ RGO) trielement composite material.
The present embodiment obtains the XRD of manganese carbonate/mangano-manganic oxide/graphene trielement composite material as shown in figure 1, from figure
It can be seen that, resulting material is divided into two kinds of compositions, and the PDF cards with mangano-manganic oxide and manganese carbonate match respectively, card
It is manganese carbonate and mangano-manganic oxide to understand resulting material.Shown in transmission plot and two kinds of particles be dispersed with graphene sheet layer,
A kind of micron ball, and it is scattered in the nanometer little particle on periphery.
Fig. 3 is the high-resolution tem analysis at the nano particle in transmission picture, finds its lattice fringe shown
Represent Mn3O4(211) crystal face.By energy spectrum analysis, the atomic ratio that can obtain manganese and oxygen is 46.8:53.2, it is approximately
3:4, represent Mn3O4。
Fig. 5 is the high-resolution tem analysis at the micron particles in transmission picture, finds its lattice fringe shown
Represent MnCO3(102) crystal face.By energy spectrum analysis, the atomic ratio that can obtain manganese and oxygen is 22.7:77.3, approximately
For 1:3, represent MnCO3。
Comparative example:The present embodiment is molten for 0.1mol/L sodium carbonate by concentration from step 3 unlike embodiment one
Liquid is slowly dropped into Mn/ graphene oxide solutions, the pH=9 of regulation system.
The present embodiment obtains manganese carbonate/graphene (MnCO3/ RGO) composite.
To MnCO3/Mn3O4/ RGO trielement composite materials carry out electrochemical property test, and wherein curve 2 is represented with circulation
Carry out specific capacity change, curve 1 represents the coulombic efficiency of the material with the change of cycle-index.Can from figure
Go out, under 1000 milliamperes every gram of current density, after 800 circulate, specific capacity can also be maintained at 532mAhg-1, simultaneously
After preceding 10 circulations, the coulombic efficiency of material is maintained at 100%.
Shown according to Fig. 8 electrochemical property test figure, wherein 3 represent MnCO3/Mn3O4/ RGO trielement composite materials, 4 generations
Table MnCO3/ RGO composites.In 100mAg-1Current density under tested.It was found that manganese carbonate/mangano-manganic oxide/graphite
Alkene trielement composite material shows higher specific capacity, while with the progress of circulation, specific capacity constantly increases, and carbonic acid
Manganese/graphene composite material is with the progress of circulation, specific capacity reduction.
Manganese carbonate/mangano-manganic oxide/graphene composite material and manganese carbonate/graphene composite material is contrasted to enclose the 15th,
Impedance curve after 51 circles, 116 circles, and 231 circles, it is known that, with the progress of circulation, manganese carbonate/mangano-manganic oxide/graphene is multiple
Condensation material has smaller impedance, electric conductivity enhancing.
Experiment shows, manganese carbonate/mangano-manganic oxide/graphene and manganese carbonate/graphene composite material are compared into hair
It is existing, there is smaller semicircle in the EIS curves of ternary material, and the slope of straight line is also more big, illustrates its electric conductivity
Enhancing, the test of simultaneous electrochemical performance also show the enhancing of its performance.Manganese carbonate/mangano-manganic oxide/graphene of the present invention
Trielement composite material is by the improvement of structure, and due to the increase of solution ph, manganese carbonate generates nanosizing, and in high ph-values
Environment in, occur in that the nano particle of mangano-manganic oxide, the structure of nanosizing is conducive to releasable material in charge and discharge process
Stress, adapt to volumetric expansion there is provided more active sites, promote reaction, enhance cycle performance and specific capacity;Simultaneously because
The presence of two kinds of active materials, generates certain synergy between them, so that the electrochemistry for promoting reaction system is moved
Mechanics so that it has higher specific capacity.
Claims (10)
1. the preparation method of manganese carbonate/mangano-manganic oxide/graphene trielement composite material, it is characterised in that this method is by following
Step is realized:
The first, 1~10g graphite be put into 23~230ml H2SO4In solution, 20~60min is stirred at 0~5 DEG C, is then added
4~40g KMnO4, 2~3h of stirring at 0~5 DEG C is maintained at, temperature is then increased to 30~45 DEG C, 2~3h is kept stirring for,
Temperature is further increased to 85~98 DEG C, continues to stir 10~30min, add 150~1500ml deionized waters and 10~
100ml H2O2, cool down and obtain Mn/ graphite oxide solutions;
2nd, the Mn/ graphite oxide solutions for obtaining step one handle 2~3h under ultrasound, obtain Mn/ graphene oxide solutions;
3rd, during stirring, sodium carbonate liquor is added dropwise in Mn/ graphene oxide solutions, the pH to 9 of regulation system~
11, obtain manganese carbonate/mangano-manganic oxide/graphene solution;
4th, manganese carbonate/mangano-manganic oxide/graphene solution that step 3 is obtained is placed in 90~98 DEG C of water-bath, keeps stirring
Mix 2~3h, be then collected by filtration precipitate and cleaned with deionized water, obtained after freeze-drying manganese carbonate/mangano-manganic oxide/
Graphene trielement composite material.
2. the preparation method of manganese carbonate/mangano-manganic oxide/graphene trielement composite material according to claim 1, it is special
Levy and be H described in step one2SO4The mass concentration of solution is 98%.
3. the preparation method of manganese carbonate/mangano-manganic oxide/graphene trielement composite material according to claim 1, it is special
Levy and be the H that the mass concentration that 1g graphite is put into 23ml is 98% by step one2SO4In solution, at 0~5 DEG C stir 20~
60min, then adds 5g KMnO4。
4. the preparation method of manganese carbonate/mangano-manganic oxide/graphene trielement composite material according to claim 1, it is special
Levy and be step 2 to handle 2~3h under 80~100W power ultrasonic.
5. the preparation method of manganese carbonate/mangano-manganic oxide/graphene trielement composite material according to claim 1, it is special
Levy and be the concentration of sodium carbonate liquor in step 3 for 0.05~0.2mol/L.
6. the preparation method of manganese carbonate/mangano-manganic oxide/graphene trielement composite material according to claim 1, it is special
Levy the pH to 10~11 for being step 3 regulation system.
7. the preparation method of manganese carbonate/mangano-manganic oxide/graphene trielement composite material according to claim 6, it is special
Levy the pH to 11 for being step 3 regulation system.
8. the preparation method of manganese carbonate/mangano-manganic oxide/graphene trielement composite material according to claim 1, it is special
Levy and be in step 4 that freeze-drying is dried in vacuo at -70 DEG C.
9. the preparation method of manganese carbonate/mangano-manganic oxide/graphene trielement composite material according to claim 1, it is special
Levy and be that manganese carbonate/mangano-manganic oxide/graphene solution is placed in 95 DEG C of water-bath by step 4, be kept stirring for 2h.
10. the application of manganese carbonate/mangano-manganic oxide/graphene trielement composite material as claimed in claim 1, it is characterised in that
It regard the manganese carbonate/mangano-manganic oxide/graphene trielement composite material as the cell negative electrode material in lithium ion battery.
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CN110600682A (en) * | 2018-06-12 | 2019-12-20 | 天津大学 | Sandwich-shaped hollow spherical lithium ion battery cathode material and preparation method thereof |
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CN110600682A (en) * | 2018-06-12 | 2019-12-20 | 天津大学 | Sandwich-shaped hollow spherical lithium ion battery cathode material and preparation method thereof |
CN110600682B (en) * | 2018-06-12 | 2022-03-01 | 天津大学 | Sandwich-shaped hollow spherical lithium ion battery cathode material and preparation method thereof |
CN110127669A (en) * | 2019-05-19 | 2019-08-16 | 吉林大学 | A kind of preparation method of redox graphene and trimanganese tetroxide nano particle hybrid aerogel |
CN110127669B (en) * | 2019-05-19 | 2022-08-09 | 吉林大学 | Preparation method of reduced graphene oxide and trimanganese tetroxide nanoparticle hybrid aerogel |
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