CN108807945A - Redox graphene/stannate anode material of lithium-ion battery and its preparation method and application - Google Patents
Redox graphene/stannate anode material of lithium-ion battery and its preparation method and application Download PDFInfo
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- CN108807945A CN108807945A CN201810842705.6A CN201810842705A CN108807945A CN 108807945 A CN108807945 A CN 108807945A CN 201810842705 A CN201810842705 A CN 201810842705A CN 108807945 A CN108807945 A CN 108807945A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of redox graphene/stannate anode material of lithium-ion batteries and its preparation method and application, this method by by the aqueous dispersion of chlorate and sodium stannate in graphene oxide solution, carry out hydro-thermal reaction, generate suspension, separation of solid and liquid obtains sediment, and sediment high-temperature calcination is obtained the former graphene oxide/stannate anode material of lithium-ion battery；The chlorate is manganese chloride, CoCL2 6H2O or zinc chloride.Compared with prior art, present invention process is simple, and process is easily controllable, and raw material is easy to get, of low cost, reproducible.There is redox graphene/stannate (stannic acid manganese, the cobaltous stannate, zinc stannate) composite construction prepared excellent electrochemistry to store up sodium performance, be good anode material of lithium-ion battery.
Description
Technical field
The present invention relates to battery material preparing technical fields, more particularly, to a kind of redox graphene/stannate sodium
Ion battery cathode material and its preparation method and application.
Background technology
As the substitute of lithium ion battery, since sodium is resourceful, at low cost, efficient, stable chemical performance etc. is excellent
Point so that sodium-ion battery causes more and more to pay close attention to.Compared with lithium ion battery, significant challenge that sodium-ion battery faces
It is to seek one suitably can effectively carry the anode material of lithium-ion battery being relatively large in diameter.Currently, some are electric in the world
Sodium-ion battery technology is classified as an important basic and perspective study field by the relatively advanced country of pool technology, and
The energy-storage battery technological development direction paid close attention to as future.Try to explore specific capacity height, have extended cycle life, security performance
Novel anode material of lithium-ion battery system good, temperature applicable range is wide has become research and development high-performance sodium ion in the world
The common problem of secondary battery electrode material.
Electrode material is that the important component of sodium-ion battery, especially negative material are the key that sodium-ion batteries.
Sodium ion negative material main research includes tin-based material, oxide, sulfide, phosphide and selenides in recent years.Its
Middle ternary oxide becomes one of hot spot of Recent study because widely being paid close attention to higher theoretical capacity.But
Ternary oxide can cause huge volume expansion in charging process, lead to serious capacity attenuation, limit its reality
Using.Therefore, it is badly in need of carrying out necessary modification to such material, its cycle performance, high rate performance etc. is promoted with comprehensive.In order to gram
These disadvantages are taken, can be used and carried out with the high carbon material of stability compound, design special structure, the stability of holding structure,
The utilization rate of active material is improved, improves battery performance, and synthesis takes into account various modified methods, to obtain excellent answer
Composite electrode material.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of reduction-oxidation graphite
Alkene/stannate anode material of lithium-ion battery and its preparation method and application.The sodium-ion battery cathode prepared through the invention
Material first charge-discharge efficiency height and stable cycle performance, and technique green is simple, it is easily prepared.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of redox graphene/stannate anode material of lithium-ion battery, this method is by by chlorine
The aqueous dispersion of salt dissolving and sodium stannate carries out hydro-thermal reaction in graphene oxide solution, generates suspension, is separated by solid-liquid separation
To sediment, sediment high-temperature calcination is obtained into the former graphene oxide/stannate anode material of lithium-ion battery；It is described
Chlorate be manganese chloride, CoCL2 6H2O or zinc chloride.
The present invention uses the combination of hydro-thermal method and calcination method：Hydro-thermal method is used to prepare the hydroxyl stannate of size uniform first
Salt；Further it is multiple to obtain redox graphene/stannate (stannic acid manganese, cobaltous stannate, zinc stannate) sodium-ion battery cathode for calcining
Condensation material.
Preferably, this approach includes the following steps：
(1) chlorination salt powder and sodium stannate are add to deionized water, form presoma, is then dispersed in graphite oxide
In alkene solution, and it is stirred until homogeneous；
(2) it is transferred in water heating kettle, carries out hydro-thermal reaction, after being cooled to room temperature, obtain suspension；
(3) suspension is separated by solid-liquid separation, obtains sediment, desciccate will be obtained after sediment washing, drying；
(4) desciccate is calcined at high temperature, obtains the former graphene oxide/stannate sodium-ion battery cathode
Material.
Preferably, the molar ratio of the chlorate and sodium stannate is 1:1, chlorination in the aqueous solution of chlorate and sodium stannate
The concentration of salt and sodium stannate is 0.005~0.1mol/L.
Preferably, the single layer rate of graphene oxide is more than 90% in the graphene oxide solution.
Preferably, a concentration of 0.1~2mg/mL of the graphene oxide solution, the solvent of graphene oxide solution are
Deionized water.
Preferably, the configuration of the graphene oxide solution uses following methods：Graphene oxide is dissolved in solvent,
Under the conditions of power is 200~700 watts, 1~5h of ultrasound obtains the graphene oxide water solution of stable homogeneous.
Preferably, mass ratio used in chlorate and graphene oxide is 3:1~6:1.Chlorate and graphene oxide institute
It is less than 3 with mass ratio:1, the redox graphene in prepared product can be caused excessive, electrical property is caused to be deteriorated, when than
Example is more than 6:1, the redox graphene in prepared product can be caused very few, its electricity can not be caused by improving electric conductivity
Degradation.
Preferably, the condition of hydro-thermal reaction be 160~200 DEG C at heating reaction 12~for 24 hours.In the temperature and reaction time
In range, impurity is less in final product, and object is relatively pure, and more uncomplicated laundering.
Preferably, it is separated by solid-liquid separation the method using filtering, uses deionized water and anhydrous second before sediment high-temperature calcination successively
Alcohol washs, and 6~12h is dried in vacuo in the environment less than 90 DEG C.The effect of washing is to remove not sufficiently reactive impurity.
Preferably, the high-temperature calcination temperature is 300~550 DEG C, and calcination atmosphere is nitrogen atmosphere, calcination time 3
~4h.
It is further preferred that the high-temperature calcination temperature is 400 DEG C, calcination atmosphere is nitrogen atmosphere, and calcination time is
200 minutes.Temperature is too low or calcination time is very few can make negative material crystallinity difference and stannate is not easy to be formed, and temperature is excessively high
Or calcination time is long to cause stannate to decompose.
The present invention also provides a kind of redox graphene being prepared using the method/stannate sodium ions
Cell negative electrode material.
The present invention also provides a kind of answering for the redox graphene/stannate anode material of lithium-ion battery
With after mixing by the redox graphene/stannate anode material of lithium-ion battery and binder and conductive agent
Coated on copper foil, sodium-ion battery negative plate is obtained after drying, roll-in.
Preferably：
The redox graphene/stannate anode material of lithium-ion battery, binder and conductive agent weight ratio are
(70~80):(20~10):10.
The binder is sodium carboxymethylcellulose.
The conductive agent is conductive carbon Super-P or conductive black.
The drying condition be 50~120 DEG C at vacuum drying 5~for 24 hours.It is dried, is not only able at such a temperature
It is preferable dry complete, and the material of coating will not be had an impact.
The thickness of the coating is 100~180 μm, and the overall thickness of the electrode slice roll-in is 75~150 μm.Upper
It states in thickness range, prepared single pole piece load-carrying is moderate, convenient for being impregnated with for electrolyte, and it is not easily to fall off.
The present invention also provides sodium-ion battery negative plates made from a kind of preparation in accordance with the present invention.
The present invention has synthesized the smaller nanostructure of size in the case where surfactant is not used；It is restored by introducing
Graphene oxide obtains nanocomposite, not only increases electric conductivity, is conducive to the diffusion of sodium ion and electronics, and in activity
Play the role of buffer layer between substance and electrolyte.Meanwhile polarization of electrode rate is reduced so as to improve the electrification of battery
Learn performance.Under 100mA/g current densities, redox graphene/stannate (stannic acid manganese, cobaltous stannate, zinc stannate) composite wood
Discharge capacity is respectively 754mAh/g, 650mAh/g, 609mAh/g to material for the first time.The present invention is synthesized using hydro-thermal method and calcination method
Redox graphene/stannate (stannic acid manganese, cobaltous stannate, zinc stannate) composite material, simple for process, process is easily controllable, former
Material is easy to get, of low cost, reproducible.Redox graphene/the stannate (stannic acid manganese, cobaltous stannate, zinc stannate) prepared
There is composite construction excellent electrochemistry to store up sodium performance, be good anode material of lithium-ion battery.
Compared with prior art, preparation method of the invention passes through solvent-thermal process redox graphene/stannate (tin
Sour manganese, cobaltous stannate, zinc stannate) anode material of lithium-ion battery, effectively improve Volumetric expansion when charge and discharge and group
Poly- effect enhances the cycle performance of material, by introducing redox graphene, enhances ternary tin base oxide material
Electric conductivity and stability, and technique is environmentally protective in preparation process.Redox graphene/stannate produced by the present invention
(stannic acid manganese, cobaltous stannate, zinc stannate) anode material of lithium-ion battery, first charge-discharge efficiency are high, and specific capacity is high, high rate performance and
It is existing irreversible when actually preparing the application of sodium-ion battery cathode to solve ternary tin base oxide material for good cycle
The problem of capacitance loss is big and poor circulation.
Description of the drawings
Fig. 1 is the anode material of lithium-ion battery powder x-ray diffraction obtained in step 3 in the embodiment of the present invention 1,2,3
Test chart；
Fig. 2 is the Raman figure of the anode material of lithium-ion battery obtained in step 3 in the embodiment of the present invention 1,2,3；
Fig. 3 is that the transmitted electron of the anode material of lithium-ion battery obtained in step 3 in the embodiment of the present invention 1,2,3 is aobvious
Micro mirror photo；
Fig. 4 is in the anode material of lithium-ion battery and comparative example 1,2,3 that step 3 obtains in the embodiment of the present invention 1,2,3
Anode material of lithium-ion battery makes the cycle performance figure of sodium-ion battery；
Fig. 5 is in the anode material of lithium-ion battery and comparative example 1,2,3 that step 3 obtains in the embodiment of the present invention 1,2,3
Anode material of lithium-ion battery makes the high rate performance figure of sodium-ion battery；
Fig. 6 is the cycle performance figure that the anode material of lithium-ion battery that comparative example 4,5,6 obtains makes sodium-ion battery；
Fig. 7 is the cycle performance figure that the anode material of lithium-ion battery that comparative example 7,8,9 obtains makes sodium-ion battery.
Specific implementation mode
A kind of preparation method of redox graphene/stannate anode material of lithium-ion battery, this method is by by chlorine
The aqueous dispersion of salt dissolving and sodium stannate carries out hydro-thermal reaction in graphene oxide solution, generates suspension, is separated by solid-liquid separation
To sediment, sediment high-temperature calcination is obtained into the former graphene oxide/stannate anode material of lithium-ion battery；It is described
Chlorate be manganese chloride, CoCL2 6H2O or zinc chloride.
The present invention uses the combination of hydro-thermal method and calcination method：Hydro-thermal method is used to prepare the hydroxyl stannate of size uniform first
Salt；Further it is multiple to obtain redox graphene/stannate (stannic acid manganese, cobaltous stannate, zinc stannate) sodium-ion battery cathode for calcining
Condensation material.
Preferably, this approach includes the following steps：
(1) chlorination salt powder and sodium stannate are add to deionized water, form presoma, is then dispersed in graphite oxide
In alkene solution, and it is stirred until homogeneous；
(2) it is transferred in water heating kettle, carries out hydro-thermal reaction, after being cooled to room temperature, obtain suspension；
(3) suspension is separated by solid-liquid separation, obtains sediment, desciccate will be obtained after sediment washing, drying；
(4) desciccate is calcined at high temperature, obtains the former graphene oxide/stannate sodium-ion battery cathode
Material.
Preferably, the molar ratio of the chlorate and sodium stannate is 1:1, chlorination in the aqueous solution of chlorate and sodium stannate
The concentration of salt and sodium stannate is 0.005~0.1mol/L.
Preferably, the single layer rate of graphene oxide is more than 90% in the graphene oxide solution.
Preferably, a concentration of 0.1~2mg/mL of the graphene oxide solution, the solvent of graphene oxide solution are
Deionized water.
Preferably, the configuration of the graphene oxide solution uses following methods：Graphene oxide is dissolved in solvent,
Under the conditions of power is 200~700 watts, 1~5h of ultrasound obtains the graphene oxide water solution of stable homogeneous.
Preferably, mass ratio used in chlorate and graphene oxide is 3:1~6:1.
Preferably, the condition of hydro-thermal reaction be 160~200 DEG C at heating reaction 12~for 24 hours.In the temperature and reaction time
In range, impurity is less in final product, and object is relatively pure, and more uncomplicated laundering.
Preferably, it is separated by solid-liquid separation the method using filtering, uses deionized water and anhydrous second before sediment high-temperature calcination successively
Alcohol washs, and 6~12h is dried in vacuo in the environment less than 90 DEG C.The effect of washing is to remove not sufficiently reactive impurity.
Preferably, the high-temperature calcination temperature is 300~550 DEG C, and calcination atmosphere is nitrogen atmosphere, calcination time 3
~4h.
It is further preferred that the high-temperature calcination temperature is 400 DEG C, calcination atmosphere is nitrogen atmosphere, and calcination time is
200 minutes.Temperature is too low or calcination time is very few can make negative material crystallinity difference and stannate is not easy to be formed, and temperature is excessively high
Or calcination time is long to cause stannate to decompose.
The present invention also provides a kind of redox graphene being prepared using the method/stannate sodium ions
Cell negative electrode material.
The present invention also provides a kind of answering for the redox graphene/stannate anode material of lithium-ion battery
With after mixing by the redox graphene/stannate anode material of lithium-ion battery and binder and conductive agent
Coated on copper foil, sodium-ion battery negative plate is obtained after drying, roll-in.
Preferably：
The redox graphene/stannate anode material of lithium-ion battery, binder and conductive agent weight ratio are
(70~80):(20~10):10.
The binder is sodium carboxymethylcellulose.
The conductive agent is conductive carbon Super-P or conductive black.
The drying condition be 50~120 DEG C at vacuum drying 5~for 24 hours.It is dried, is not only able at such a temperature
It is preferable dry complete, and the material of coating will not be had an impact.
The thickness of the coating is 100~180 μm, and the overall thickness of the electrode slice roll-in is 75~150 μm.Upper
It states in thickness range, prepared single pole piece load-carrying is moderate, convenient for being impregnated with for electrolyte, and it is not easily to fall off.
The present invention also provides sodium-ion battery negative plates made from a kind of preparation in accordance with the present invention.
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
In the present embodiment, a kind of redox graphene/stannate (stannic acid manganese) anode material of lithium-ion battery preparation side
Method includes the following steps：
Step 1: 0.5mmol manganese chlorides, 0.5mmol sodium stannates is taken to be dissolved in 10mL deionized waters first, 2h is stirred, then
Adding 20mL graphene oxide solutions, (20mg graphene oxides are dissolved in 20mL deionized waters, under the conditions of power is 300w, surpass
Sound cleans 3h), magnetic agitation 1h thereafter；
Step 2: being then transferred into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, reaction is heated under conditions of 180 DEG C
24h.It is cooled to room temperature, obtains suspension；
Step 3: suspension obtains sediment in filtration step two, sediment passes through deionized water successively, absolute ethyl alcohol is washed
It washs three times；It is dried in vacuo 12h in 60 DEG C of environment.Obtain redox graphene/stannate (stannic acid manganese) battery cathode material
Material.
Step 4: the product that step 3 is obtained is in a nitrogen atmosphere, 200min is calcined at 400 DEG C, you can restored
Graphene oxide/stannate (stannic acid manganese) cell negative electrode material.
The present embodiment additionally provides a kind of preparation method of sodium-ion battery negative plate.Specifically, by this implementation of 0.02g
The binder carboxylic first of redox graphene/stannate (stannic acid manganese) anode material of lithium-ion battery and 0.0025g made from example
Base sodium cellulosate, 0.0025g conductive agent Super-P uniformly mix, using water as solvent, be tuned into slurry, be coated in copper foil
Upper (thickness of coating is 150 μm), and through 110 DEG C of dry 12h of vacuum, roll-in (thickness of roll-in is 130 μm), be prepared into sodium from
Sub- battery cathode sheet.Sodium-ion battery negative plate made from the present embodiment, metallic sodium piece, electrolyte are assembled into sodium ion electricity
Pond, for carrying out constant current charge-discharge test, used electrolyte is to contain 1.0M NaClO4EC/DEC/FEC (1:1:
2Vol%).
Embodiment 2
In the present embodiment, a kind of redox graphene/stannate (cobaltous stannate) anode material of lithium-ion battery preparation side
Method includes the following steps：
Step 1: 0.5mmol CoCL2 6H2Os, 0.5mmol sodium stannates is taken to be dissolved in 10mL deionized waters first, 2h is stirred,
Then adding 20mL graphene oxide solutions, (20mg graphene oxides are dissolved in 20mL deionized waters, are 300w conditions in power
Under, it is cleaned by ultrasonic 3h), magnetic agitation 1h thereafter；
Step 2: being then transferred into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, reaction is heated under conditions of 180 DEG C
24h.It is cooled to room temperature, obtains suspension；
Step 3: suspension obtains sediment in filtration step two, sediment passes through deionized water successively, absolute ethyl alcohol is washed
It washs three times；It is dried in vacuo 12h in 60 DEG C of environment.Obtain redox graphene/stannate (cobaltous stannate) battery cathode material
Material.
Step 4: the product that step 3 is obtained is in a nitrogen atmosphere, 200min is calcined at 400 DEG C, you can restored
Graphene oxide/stannate (cobaltous stannate) cell negative electrode material.
The present embodiment additionally provides a kind of preparation method of sodium-ion battery negative plate.Specifically, by this implementation of 0.02g
The binder carboxylic first of redox graphene/stannate (cobaltous stannate) anode material of lithium-ion battery and 0.0025g made from example
Base sodium cellulosate, 0.0025g conductive agent Super-P uniformly mix, using water as solvent, be tuned into slurry, be coated in copper foil
Upper (thickness of coating is 150 μm), and through 110 DEG C of dry 12h of vacuum, roll-in (thickness of roll-in is 130 μm), be prepared into sodium from
Sub- battery cathode sheet.Sodium-ion battery negative plate made from the present embodiment, metallic sodium piece, electrolyte are assembled into sodium ion electricity
Pond, for carrying out constant current charge-discharge test, used electrolyte is to contain 1.0M NaClO4EC/DEC/FEC (1:1:
2Vol%).
Embodiment 3
In the present embodiment, a kind of redox graphene/stannate (zinc stannate) anode material of lithium-ion battery preparation side
Method includes the following steps：
Step 1: 0.5mmol zinc chloride, 0.5mmol sodium stannates is taken to be dissolved in 10mL deionized waters first, 2h is stirred, then
Adding 20mL graphene oxide solutions, (20mg graphene oxides are dissolved in 20mL deionized waters, under the conditions of power is 300w, surpass
Sound cleans 3h), magnetic agitation 1h thereafter；
Step 2: being then transferred into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, reaction is heated under conditions of 180 DEG C
24h.It is cooled to room temperature, obtains suspension；
Step 3: suspension obtains sediment in filtration step two, sediment passes through deionized water successively, absolute ethyl alcohol is washed
It washs three times；It is dried in vacuo 12h in 60 DEG C of environment.Obtain redox graphene/stannate (zinc stannate) battery cathode material
Material.
Step 4: the product that step 3 is obtained is in a nitrogen atmosphere, 200min is calcined at 400 DEG C, you can restored
Graphene oxide/stannate (zinc stannate) cell negative electrode material.
The present embodiment additionally provides a kind of preparation method of sodium-ion battery negative plate.Specifically, by this implementation of 0.02g
The binder carboxylic first of redox graphene/stannate (zinc stannate) anode material of lithium-ion battery and 0.0025g made from example
Base sodium cellulosate, 0.0025g conductive agent Super-P uniformly mix, using water as solvent, be tuned into slurry, be coated in copper foil
Upper (thickness of coating is 150 μm), and through 110 DEG C of dry 12h of vacuum, roll-in (thickness of roll-in is 130 μm), be prepared into sodium from
Sub- battery cathode sheet.Sodium-ion battery negative plate made from the present embodiment, metallic sodium piece, electrolyte are assembled into sodium ion electricity
Pond, for carrying out constant current charge-discharge test, used electrolyte is to contain 1.0M NaClO4EC/DEC/FEC (1:1:
2Vol%).
Embodiment 4
The present embodiment is substantially the same manner as Example 1, the difference is that, in the present embodiment, graphene oxide solution it is dense
Degree is 0.5mg/mL, and wherein the quality of graphene oxide is the 1/3 of manganese chloride quality,.The oxygen reduction that the present embodiment is prepared
Graphite alkene/stannate (stannic acid manganese) anode material of lithium-ion battery first charge-discharge efficiency is high, and specific capacity is high, high rate performance and
Good cycle.
Embodiment 5
The present embodiment is substantially the same manner as Example 1, the difference is that, in the present embodiment, graphene oxide solution it is dense
Degree is 1.5mg/mL, and wherein the quality of graphene oxide is the 1/6 of manganese chloride quality.The reduction-oxidation that the present embodiment is prepared
Graphene/stannate (stannic acid manganese) anode material of lithium-ion battery first charge-discharge efficiency is high, and specific capacity is high, high rate performance and follows
Ring performance is good.
Embodiment 6
The present embodiment is substantially the same manner as Example 1, the difference is that, in the present embodiment, graphene oxide solution it is dense
Degree is 2mg/mL, and wherein the quality of graphene oxide is the 1/4 of manganese chloride quality.The oxygen reduction fossil that the present embodiment is prepared
Black alkene/stannate (stannic acid manganese) anode material of lithium-ion battery first charge-discharge efficiency is high, and specific capacity is high, high rate performance and cycle
Performance is good.
Embodiment 7
The present embodiment is substantially the same manner as Example 1, the difference is that, in the present embodiment, graphene oxide solution it is dense
Degree is 0.1mg/mL, and wherein the quality of graphene oxide is the 1/3 of manganese chloride quality.The reduction-oxidation that the present embodiment is prepared
Graphene/stannate (stannic acid manganese) anode material of lithium-ion battery first charge-discharge efficiency is high, and specific capacity is high, high rate performance and follows
Ring performance is good.
Embodiment 8
The present embodiment is substantially the same manner as Example 1, the difference is that, in the present embodiment, the water of chlorate and sodium stannate
The concentration of Chlorine in Solution manganese and sodium stannate is 0.1mol/L.Redox graphene/stannic acid that the present embodiment is prepared
Salt (stannic acid manganese) anode material of lithium-ion battery first charge-discharge efficiency is high, and specific capacity is high, high rate performance and good cycle.
Embodiment 9
The present embodiment is substantially the same manner as Example 1, the difference is that, in the present embodiment, the water of chlorate and sodium stannate
The concentration of Chlorine in Solution manganese and sodium stannate is 0.005mol/L.Redox graphene/tin that the present embodiment is prepared
Hydrochlorate (stannic acid manganese) anode material of lithium-ion battery first charge-discharge efficiency is high, and specific capacity is high, high rate performance and good cycle.
Embodiment 10
The present embodiment is substantially the same manner as Example 1, the difference is that, in the present embodiment, the condition of hydro-thermal reaction is 200
12h at DEG C.Anode material of lithium-ion battery is for the first time for redox graphene/stannate (stannic acid manganese) that the present embodiment is prepared
Efficiency for charge-discharge is high, and specific capacity is high, high rate performance and good cycle.
Embodiment 11
The present embodiment is substantially the same manner as Example 1, the difference is that, in the present embodiment, the condition of hydro-thermal reaction is 160
18h at DEG C.Anode material of lithium-ion battery is for the first time for redox graphene/stannate (stannic acid manganese) that the present embodiment is prepared
Efficiency for charge-discharge is high, and specific capacity is high, high rate performance and good cycle.
Embodiment 12
The present embodiment is substantially the same manner as Example 1, the difference is that, in the present embodiment, high-temperature calcination temperature is 300
DEG C, calcination atmosphere is nitrogen atmosphere, and calcination time is 400 minutes.Redox graphene/stannic acid that the present embodiment is prepared
Salt (stannic acid manganese) anode material of lithium-ion battery first charge-discharge efficiency is high, and specific capacity is high, high rate performance and good cycle.
Embodiment 13
The present embodiment is substantially the same manner as Example 1, the difference is that, in the present embodiment, high-temperature calcination temperature is 550
DEG C, calcination atmosphere is nitrogen atmosphere, and calcination time is 3 minutes.Redox graphene/stannate that the present embodiment is prepared
(stannic acid manganese) anode material of lithium-ion battery first charge-discharge efficiency is high, and specific capacity is high, high rate performance and good cycle.
Embodiment 14
The present embodiment is substantially the same manner as Example 1, the difference is that, in the present embodiment, by redox graphene/tin
Hydrochlorate anode material of lithium-ion battery, binder and conductive agent are 80 according to weight ratio:20:10 mass ratio mixing, is coated on
On copper foil, coating thickness is 100 μm, and dry temperature is 90 DEG C, drying time 12h.The overall thickness of electrode slice is after roll-in
75μm。
Embodiment 15
The present embodiment is substantially the same manner as Example 1, the difference is that, in the present embodiment, by redox graphene/tin
Hydrochlorate anode material of lithium-ion battery, binder and conductive agent are 70 according to weight ratio:10:10 mass ratio mixing, is coated on
On copper foil, coating thickness is 150 μm, and dry temperature is 50 DEG C, and drying time is for 24 hours.The overall thickness of electrode slice is after roll-in
120μm。
Embodiment 16
The present embodiment is substantially the same manner as Example 1, the difference is that, in the present embodiment, by redox graphene/tin
Hydrochlorate anode material of lithium-ion battery, binder and conductive agent are 75 according to weight ratio:15:10 mass ratio mixing, is coated on
On copper foil, coating thickness is 180 μm, and dry temperature is 120 DEG C, and drying time 5h, the overall thickness of electrode slice is after roll-in
150μm。
Comparative example 1
In this comparative example, stannic acid manganese is directly prepared as anode material of lithium-ion battery.Except being not added with oxidation stone in step 1
Outside black alkene solution, other steps are identical.Specifically, 0.5mmol manganese chlorides, 0.5mmol sodium stannates is taken to be dissolved in 20mL deionized waters,
2h is stirred, is then transferred into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, heating reaction 20h under conditions of 180 DEG C.Then
It is washed with deionization, absolute ethyl alcohol, finally in a nitrogen atmosphere, 200min is calcined at 400 DEG C.This comparative example additionally provides one kind
The preparation method of sodium-ion battery negative plate.Specifically, by the stannic acid manganese anode material of lithium-ion battery and 0.0025g of 0.02g
Binder sodium carboxymethylcellulose, 0.0025g conductive agent Super-P uniformly mix, using water as solvent, be slurred
Material is coated on copper foil (thickness of coating is 150 μm), and (thickness of roll-in is 130 μ through 110 DEG C of dry 10h of vacuum, roll-in
M) it is prepared into sodium-ion battery negative plate.By sodium-ion battery negative plate made from this comparative example, metallic sodium piece, electrolyte assembling
At sodium-ion battery, for carrying out constant current charge-discharge test, used electrolyte is to contain 1.0MNaClO4EC/DEC/FEC
(1:1:2Vol%).
Comparative example 2
In this comparative example, cobaltous stannate is directly prepared as anode material of lithium-ion battery.Except being not added with oxidation stone in step 1
Outside black alkene solution, other steps are identical.Specifically, take 0.5mmol CoCL2 6H2Os, 0.5mmol sodium stannates be dissolved in 20mL go from
Sub- water stirs 2h, is then transferred into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, and reaction is heated under conditions of 180 DEG C
20h.Then it is washed with deionization, absolute ethyl alcohol, finally in a nitrogen atmosphere, 200min is calcined at 400 DEG C.This comparative example also carries
A kind of preparation method of sodium-ion battery negative plate is supplied.Specifically, by the cobaltous stannate anode material of lithium-ion battery of 0.02g with
The binder sodium carboxymethylcellulose of 0.0025g, the conductive agent Super-P of 0.0025g are uniformly mixed, using water as solvent,
It is tuned into slurry, is coated on copper foil (thickness of coating is 150 μm), and through vacuum 110 DEG C of dry 10h, roll-in (thickness of roll-in
It is 130 μm) it is prepared into sodium-ion battery negative plate.By sodium-ion battery negative plate made from this comparative example, metallic sodium piece, electrolysis
Liquid is assembled into sodium-ion battery, and for carrying out constant current charge-discharge test, used electrolyte is to contain 1.0MNaClO4EC/
DEC/FEC(1:1:2Vol%).
Comparative example 3
In this comparative example, zinc stannate is directly prepared as anode material of lithium-ion battery.Except being not added with oxidation stone in step 1
Outside black alkene solution, other steps are identical.Specifically, 0.5mmol zinc chloride, 0.5mmol sodium stannates is taken to be dissolved in 20mL deionized waters,
2h is stirred, is then transferred into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, heating reaction 20h under conditions of 180 DEG C.Then
It is washed with deionization, absolute ethyl alcohol, finally in a nitrogen atmosphere, 200min is calcined at 400 DEG C.This comparative example additionally provides one kind
The preparation method of sodium-ion battery negative plate.Specifically, by the zinc stannate anode material of lithium-ion battery and 0.0025g of 0.02g
Binder sodium carboxymethylcellulose, 0.0025g conductive agent Super-P uniformly mix, using water as solvent, be slurred
Material is coated on copper foil (thickness of coating is 150 μm), and (thickness of roll-in is 130 μ through 110 DEG C of dry 10h of vacuum, roll-in
M) it is prepared into sodium-ion battery negative plate.By sodium-ion battery negative plate made from this comparative example, metallic sodium piece, electrolyte assembling
At sodium-ion battery, for carrying out constant current charge-discharge test, used electrolyte is to contain 1.0MNaClO4EC/DEC/FEC
(1:1:2Vol%).
Comparative example 4
In this comparative example, a kind of redox graphene/stannate (stannic acid manganese) anode material of lithium-ion battery preparation side
Method includes the following steps：
Step 1: 0.1mmol manganese chlorides, 0.1mmol sodium stannates is taken to be dissolved in 10mL deionized waters first, 2h is stirred, then
Adding 20mL graphene oxide solutions, (20mg graphene oxides are dissolved in 20mL deionized waters, under the conditions of power is 300w, surpass
Sound cleans 2h), magnetic agitation 1h thereafter；
Step 2: being then transferred into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, reaction is heated under conditions of 180 DEG C
24h.It is cooled to room temperature, obtains suspension；
Step 3: suspension obtains sediment in filtration step two, sediment passes through deionized water successively, absolute ethyl alcohol is washed
It washs three times；It is dried in vacuo 12h in 60 DEG C of environment.Obtain redox graphene/stannate (stannic acid manganese) battery cathode material
Material.
Step 4: the product that step 3 is obtained is in a nitrogen atmosphere, 200min is calcined at 400 DEG C, you can restored
Graphene oxide/stannate (stannic acid manganese) cell negative electrode material.
This comparative example additionally provides a kind of preparation method of sodium-ion battery negative plate.Specifically, by this implementation of 0.02g
The binder carboxylic first of redox graphene/stannate (stannic acid manganese) anode material of lithium-ion battery and 0.0025g made from example
Base sodium cellulosate, 0.0025g conductive agent Super-P uniformly mix, using water as solvent, be tuned into slurry, be coated in copper foil
Upper (thickness of coating is 150 μm), and through 110 DEG C of dry 12h of vacuum, roll-in (thickness of roll-in is 130 μm), be prepared into sodium from
Sub- battery cathode sheet.Sodium-ion battery negative plate made from this comparative example, metallic sodium piece, electrolyte are assembled into sodium ion electricity
Pond, for carrying out constant current charge-discharge test, used electrolyte is to contain 1.0M NaClO4EC/DEC/FEC (1:1:
2Vol%).
Comparative example 5
In this comparative example, a kind of redox graphene/stannate (cobaltous stannate) anode material of lithium-ion battery preparation side
Method includes the following steps：
Step 1: 0.1mmol CoCL2 6H2Os, 0.1mmol sodium stannates is taken to be dissolved in 10mL deionized waters first, 2h is stirred,
Then adding 20mL graphene oxide solutions, (20mg graphene oxides are dissolved in 20mL deionized waters, are 300w conditions in power
Under, it is cleaned by ultrasonic 2h), magnetic agitation 1h thereafter；
Step 2: being then transferred into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, reaction is heated under conditions of 180 DEG C
24h.It is cooled to room temperature, obtains suspension；
Step 3: suspension obtains sediment in filtration step two, sediment passes through deionized water successively, absolute ethyl alcohol is washed
It washs three times；It is dried in vacuo 12h in 60 DEG C of environment.Obtain redox graphene/stannate (cobaltous stannate) battery cathode material
Material.
Step 4: the product that step 3 is obtained is in a nitrogen atmosphere, 200min is calcined at 400 DEG C, you can restored
Graphene oxide/stannate (cobaltous stannate) cell negative electrode material.
This comparative example additionally provides a kind of preparation method of sodium-ion battery negative plate.Specifically, by this implementation of 0.02g
The binder carboxylic first of redox graphene/stannate (cobaltous stannate) anode material of lithium-ion battery and 0.0025g made from example
Base sodium cellulosate, 0.0025g conductive agent Super-P uniformly mix, using water as solvent, be tuned into slurry, be coated in copper foil
Upper (thickness of coating is 150 μm), and through 110 DEG C of dry 12h of vacuum, roll-in (thickness of roll-in is 130 μm), be prepared into sodium from
Sub- battery cathode sheet.Sodium-ion battery negative plate made from this comparative example, metallic sodium piece, electrolyte are assembled into sodium ion electricity
Pond, for carrying out constant current charge-discharge test, used electrolyte is to contain 1.0M NaClO4EC/DEC/FEC (1:1:
2Vol%).
Comparative example 6
In this comparative example, a kind of redox graphene/stannate (zinc stannate) anode material of lithium-ion battery preparation side
Method includes the following steps：
Step 1: 0.1mmol zinc chloride, 0.1mmol sodium stannates is taken to be dissolved in 10mL deionized waters first, 2h is stirred, then
Adding 20mL graphene oxide solutions, (20mg graphene oxides are dissolved in 20mL deionized waters, under the conditions of power is 300w, surpass
Sound cleans 2h), magnetic agitation 1h thereafter；
Step 2: being then transferred into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, reaction is heated under conditions of 180 DEG C
24h.It is cooled to room temperature, obtains suspension；
Step 3: suspension obtains sediment in filtration step two, sediment passes through deionized water successively, absolute ethyl alcohol is washed
It washs three times；It is dried in vacuo 12h in 60 DEG C of environment.Obtain redox graphene/stannate (zinc stannate) battery cathode material
Material.
Step 4: the product that step 3 is obtained is in a nitrogen atmosphere, 200min is calcined at 400 DEG C, you can restored
Graphene oxide/stannate (zinc stannate) cell negative electrode material.
This comparative example additionally provides a kind of preparation method of sodium-ion battery negative plate.Specifically, by this implementation of 0.02g
The binder carboxylic first of redox graphene/stannate (zinc stannate) anode material of lithium-ion battery and 0.0025g made from example
Base sodium cellulosate, 0.0025g conductive agent Super-P uniformly mix, using water as solvent, be tuned into slurry, be coated in copper foil
Upper (thickness of coating is 150 μm), and through 110 DEG C of dry 12h of vacuum, roll-in (thickness of roll-in is 130 μm), be prepared into sodium from
Sub- battery cathode sheet.Sodium-ion battery negative plate made from this comparative example, metallic sodium piece, electrolyte are assembled into sodium ion electricity
Pond, for carrying out constant current charge-discharge test, used electrolyte is to contain 1.0M NaClO4EC/DEC/FEC (1:1:
2Vol%).
Comparative example 7
In this comparative example, a kind of redox graphene/stannate (stannic acid manganese) anode material of lithium-ion battery preparation side
Method includes the following steps：
Step 1: 1mmol manganese chlorides, 1mmol sodium stannates is taken to be dissolved in 10mL deionized waters first, 2h is stirred, is then added again
Entering 20mL graphene oxide solutions, (20mg graphene oxides are dissolved in 20mL deionized waters, and under the conditions of power is 300w, ultrasound is clear
Wash 2h), magnetic agitation 1h thereafter；
Step 2: being then transferred into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, reaction is heated under conditions of 180 DEG C
24h.It is cooled to room temperature, obtains suspension；
Step 3: suspension obtains sediment in filtration step two, sediment passes through deionized water successively, absolute ethyl alcohol is washed
It washs three times；It is dried in vacuo 12h in 60 DEG C of environment.Obtain redox graphene/stannate (stannic acid manganese) battery cathode material
Material.
Step 4: the product that step 3 is obtained is in a nitrogen atmosphere, 200min is calcined at 400 DEG C, you can restored
Graphene oxide/stannate (stannic acid manganese) cell negative electrode material.
This comparative example additionally provides a kind of preparation method of sodium-ion battery negative plate.Specifically, by this implementation of 0.02g
The binder carboxylic first of redox graphene/stannate (stannic acid manganese) anode material of lithium-ion battery and 0.0025g made from example
Base sodium cellulosate, 0.0025g conductive agent Super-P uniformly mix, using water as solvent, be tuned into slurry, be coated in copper foil
Upper (thickness of coating is 150 μm), and through 110 DEG C of dry 12h of vacuum, roll-in (thickness of roll-in is 130 μm), be prepared into sodium from
Sub- battery cathode sheet.Sodium-ion battery negative plate made from this comparative example, metallic sodium piece, electrolyte are assembled into sodium ion electricity
Pond, for carrying out constant current charge-discharge test, used electrolyte is the EC/DEC/FEC (1 containing 1.0M NaClO4:1:
2Vol%).
Comparative example 8
In this comparative example, a kind of redox graphene/stannate (cobaltous stannate) anode material of lithium-ion battery preparation side
Method includes the following steps：
Step 1: 1mmol CoCL2 6H2Os, 1mmol sodium stannates is taken to be dissolved in 10mL deionized waters first, 2h is stirred, then
Adding 20mL graphene oxide solutions, (20mg graphene oxides are dissolved in 20mL deionized waters, under the conditions of power is 300w, surpass
Sound cleans 2h), magnetic agitation 1h thereafter；
Step 2: being then transferred into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, reaction is heated under conditions of 180 DEG C
24h.It is cooled to room temperature, obtains suspension；
Step 3: suspension obtains sediment in filtration step two, sediment passes through deionized water successively, absolute ethyl alcohol is washed
It washs three times；It is dried in vacuo 12h in 60 DEG C of environment.Obtain redox graphene/stannate (cobaltous stannate) battery cathode material
Material.
Step 4: the product that step 3 is obtained is in a nitrogen atmosphere, 200min is calcined at 400 DEG C, you can restored
Graphene oxide/stannate (cobaltous stannate) cell negative electrode material.
This comparative example additionally provides a kind of preparation method of sodium-ion battery negative plate.Specifically, by this implementation of 0.02g
The binder carboxylic first of redox graphene/stannate (cobaltous stannate) anode material of lithium-ion battery and 0.0025g made from example
Base sodium cellulosate, 0.0025g conductive agent Super-P uniformly mix, using water as solvent, be tuned into slurry, be coated in copper foil
Upper (thickness of coating is 150 μm), and through 110 DEG C of dry 12h of vacuum, roll-in (thickness of roll-in is 130 μm), be prepared into sodium from
Sub- battery cathode sheet.Sodium-ion battery negative plate made from this comparative example, metallic sodium piece, electrolyte are assembled into sodium ion electricity
Pond, for carrying out constant current charge-discharge test, used electrolyte is the EC/DEC/FEC (1 containing 1.0M NaClO4:1:
2Vol%).
Comparative example 9
In this comparative example, a kind of redox graphene/stannate (zinc stannate) anode material of lithium-ion battery preparation side
Method includes the following steps：
Step 1: 1mmol zinc chloride, 1mmol sodium stannates is taken to be dissolved in 10mL deionized waters first, 2h is stirred, is then added again
Entering 20mL graphene oxide solutions, (20mg graphene oxides are dissolved in 20mL deionized waters, and under the conditions of power is 300w, ultrasound is clear
Wash 2h), magnetic agitation 1h thereafter；
Step 2: being then transferred into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, reaction is heated under conditions of 180 DEG C
24h.It is cooled to room temperature, obtains suspension；
Step 3: suspension obtains sediment in filtration step two, sediment passes through deionized water successively, absolute ethyl alcohol is washed
It washs three times；It is dried in vacuo 12h in 60 DEG C of environment.Obtain redox graphene/stannate (zinc stannate) battery cathode material
Material.
Step 4: the product that step 3 is obtained is in a nitrogen atmosphere, 200min is calcined at 400 DEG C, you can restored
Graphene oxide/stannate (zinc stannate) cell negative electrode material.
This comparative example additionally provides a kind of preparation method of sodium-ion battery negative plate.Specifically, by this implementation of 0.02g
The binder carboxylic first of redox graphene/stannate (zinc stannate) anode material of lithium-ion battery and 0.0025g made from example
Base sodium cellulosate, 0.0025g conductive agent Super-P uniformly mix, using water as solvent, be tuned into slurry, be coated in copper foil
Upper (thickness of coating is 150 μm), and through 110 DEG C of dry 12h of vacuum, roll-in (thickness of roll-in is 130 μm), be prepared into sodium from
Sub- battery cathode sheet.Sodium-ion battery negative plate made from this comparative example, metallic sodium piece, electrolyte are assembled into sodium ion electricity
Pond, for carrying out constant current charge-discharge test, used electrolyte is the EC/DEC/FEC (1 containing 1.0M NaClO4:1:
2Vol%).
Measure of merit compares
Material phase analysis is carried out using D2-Phaser X-ray diffractometers and obtains XRD diagram, radiation source Cu targets KαRay, λ=
0.15406nm, the pipe pressure in test process are 40kV, and Guan Liuwei 40mA, sweep speed is 5 °/min；Using LabRAMAramis
Raman optical detector is analyzed to obtain Raman figure；TEM is obtained using JEM-2100F high resolution transmission electron microscopies observation pattern
Figure；Constant current charge-discharge test is carried out using the new Weir Neware CT-3008 battery test systems in Shenzhen and obtains constant current charge-discharge
It can figure, high rate performance figure.
Fig. 1 be embodiment 1,2,3 made from redox graphene/stannate (stannic acid manganese, cobaltous stannate, zinc stannate) sodium from
The XRD diagram of sub- cell negative electrode material.
Fig. 2 be embodiment 1,2,3 made from redox graphene/stannate (stannic acid manganese, cobaltous stannate, zinc stannate) sodium from
Stannic acid manganese that sub- cell negative electrode material and comparative example 1,2,3 are prepared, cobaltous stannate, zinc stannate anode material of lithium-ion battery
Raman figure, from figure 2 it can be seen that redox graphene is introduced into, to confirm redox graphene in embodiment
1, the presence in 2,3 composite materials.
Fig. 3 be embodiment 1,2,3 made from redox graphene/stannate (stannic acid manganese, cobaltous stannate, zinc stannate) sodium from
The TEM of sub- cell negative electrode material schemes, from figure 3, it can be seen that being the reduction-oxidation graphite of nano particle prepared by embodiment 1
Alkene/stannate (stannic acid manganese) anode material of lithium-ion battery, be prepared by embodiment 2 cubical redox graphene/
Stannate (cobaltous stannate) anode material of lithium-ion battery is cubical redox graphene/stannic acid prepared by embodiment 3
Salt (zinc stannate) anode material of lithium-ion battery.
Fig. 4 be embodiment 1,2,3 made from redox graphene/stannate (stannic acid manganese, cobaltous stannate, zinc stannate) sodium from
Stannic acid manganese that sub- cell negative electrode material and comparative example 1,2,3 are prepared, cobaltous stannate, zinc stannate anode material of lithium-ion battery
Cycle performance figure, figure 4, it is seen that carrying out constant current charge-discharge test under the current density of 100mA/g, potential window is
0.01~3V, redox graphene/stannate (stannic acid manganese, cobaltous stannate, zinc stannate) anode material of lithium-ion battery are put for the first time
Electric specific capacity is up to 754mAh/g, 650mAh/g, 609mAh/g respectively, is recycled to the 100th week, specific discharge capacity is respectively maintained at
236mAh/g,281mAh/g,322mAh/g.And stannic acid manganese, cobaltous stannate, zinc stannate negative material recycle 100 difference and are only left
19mAh/g, 92mAh/g, 87mAh/g, poor circulation.Stannic acid manganese, cobaltous stannate, the stannic acid being prepared with comparative example 1,2,3
Zinc anode material of lithium-ion battery compares, and illustrates redox graphene/stannate (stannic acid that embodiment 1,2,3 is prepared
Manganese, cobaltous stannate, zinc stannate) anode material of lithium-ion battery have good cycle performance.
Fig. 5 is redox graphene/stannate (stannic acid manganese, cobaltous stannate, zinc stannate) that embodiment 1,2,3 is prepared
Stannic acid manganese, cobaltous stannate, the zinc stannate sodium-ion battery cathode material that anode material of lithium-ion battery is prepared with comparative example 1,2,3
The high rate performance figure of material, from figure 5 it can be seen that at high current 1000mA/g, oxygen reduction that embodiment 1,2,3 is prepared
Graphite alkene/stannate (stannic acid manganese, cobaltous stannate, zinc stannate) anode material of lithium-ion battery specific discharge capacity still has respectively
175mAh/g, 159mAh/g, 195mAh/g show the redox graphene/stannate (stannic acid manganese, cobaltous stannate, zinc stannate)
Anode material of lithium-ion battery has good high rate performance.
Fig. 6 be comparative example 4,5,6 made from redox graphene/stannate (stannic acid manganese, cobaltous stannate, zinc stannate) sodium from
The cycle performance figure of sub- cell negative electrode material, from fig. 6 it can be seen that carrying out constant current charge and discharge under the current density of 100mA/g
Electrical testing, potential window are 0.01~3V, redox graphene/stannate (stannic acid manganese, cobaltous stannate, zinc stannate) sodium ion electricity
Pond negative material first discharge specific capacity is respectively 570mAh/g, 595mAh/g, 509mAh/g, is recycled to the 100th week, and discharge ratio
Capacity is respectively maintained at 25mAh/g, 202mAh/g, 232mAh/g.With comparative example 4,5,6 be prepared redox graphene/
Stannate (stannic acid manganese, cobaltous stannate, zinc stannate) anode material of lithium-ion battery compares, and illustrates what embodiment 1,2,3 was prepared
Redox graphene/stannate (stannic acid manganese, cobaltous stannate, zinc stannate) anode material of lithium-ion battery has good cyclicity
Energy.
Fig. 7 be comparative example 7,8,9 made from redox graphene/stannate (stannic acid manganese, cobaltous stannate, zinc stannate) sodium from
The cycle performance figure of sub- cell negative electrode material, it can be seen from figure 7 that carrying out constant current charge and discharge under the current density of 100mA/g
Electrical testing, potential window are 0.01~3V, redox graphene/stannate (stannic acid manganese, cobaltous stannate, zinc stannate) sodium ion electricity
Pond negative material first discharge specific capacity is respectively 525mAh/g, 556mAh/g, 554mAh/g, is recycled to the 100th week, and discharge ratio
Capacity is respectively maintained at 216mAh/g, 230mAh/g, 288mAh/g.With comparative example 7,8,9 be prepared redox graphene/
Stannate (stannic acid manganese, cobaltous stannate, zinc stannate) anode material of lithium-ion battery compares, and illustrates what embodiment 1,2,3 was prepared
Redox graphene/stannate (stannic acid manganese, cobaltous stannate, zinc stannate) anode material of lithium-ion battery has good cyclicity
Energy.
Compared with the existing technology, preparation method of the invention by hydro-thermal method and calcination method synthesize redox graphene/
Stannate (stannic acid manganese, cobaltous stannate, zinc stannate), Volumetric expansion when effectively improving charge and discharge cycles are imitated with reunion
It answers, enhances the cycle performance of material, by introducing redox graphene, enhance the conduction of ternary tin base oxide material
Property and stability, and technique is environmentally protective in preparation process.Redox graphene produced by the present invention/stannate (tin
Sour manganese, cobaltous stannate, zinc stannate) anode material of lithium-ion battery first charge-discharge efficiency height, specific capacity height, high rate performance and cycle
Performance is good, solves ternary tin base oxide material existing irreversible appearance when actually preparing the application of sodium-ion battery cathode
Amount loses the problem of big and electric conductivity and poor circulation.
The above-mentioned description to embodiment is for ease of ordinary skill in the art to understand and use the invention.It is ripe
The personnel for knowing art technology obviously easily can make various modifications to these embodiments, and general original described herein
It ought to use in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, this field
Technical staff's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be in the guarantors of the present invention
Within the scope of shield.
Claims (10)
1. a kind of preparation method of redox graphene/stannate anode material of lithium-ion battery, which is characterized in that this method
By the way that by the aqueous dispersion of chlorate and sodium stannate, in graphene oxide solution, progress hydro-thermal reaction generates suspension, Gu
Sediment high-temperature calcination is obtained the former graphene oxide/stannate sodium-ion battery cathode by the isolated sediment of liquid
Material；The chlorate is manganese chloride, CoCL2 6H2O or zinc chloride.
2. the preparation method of redox graphene according to claim 1/stannate anode material of lithium-ion battery,
It is characterized in that, this approach includes the following steps：
(1) chlorination salt powder and sodium stannate are add to deionized water, form presoma, it is molten is then dispersed in graphene oxide
In liquid, and it is stirred until homogeneous；
(2) it is transferred in water heating kettle, carries out hydro-thermal reaction, after being cooled to room temperature, obtain suspension；
(3) suspension is separated by solid-liquid separation, obtains sediment, desciccate will be obtained after sediment washing, drying；
(4) desciccate is calcined at high temperature, obtains the former graphene oxide/stannate sodium-ion battery cathode material
Material.
3. the preparation side of redox graphene according to claim 1 or 2/stannate anode material of lithium-ion battery
Method, which is characterized in that the molar ratio of the chlorate and sodium stannate is 1:1, chlorination in the aqueous solution of chlorate and sodium stannate
The concentration of salt and sodium stannate is 0.005~0.1mol/L.
4. the preparation side of redox graphene according to claim 1 or 2/stannate anode material of lithium-ion battery
Method, which is characterized in that a concentration of 0.1~2mg/mL of the graphene oxide solution, the solvent of graphene oxide solution are
Deionized water.
5. the preparation side of redox graphene according to claim 1 or 2/stannate anode material of lithium-ion battery
Method, which is characterized in that mass ratio used in chlorate and graphene oxide is 3:1~6:1.
6. the preparation side of redox graphene according to claim 1 or 2/stannate anode material of lithium-ion battery
Method, which is characterized in that the condition of hydro-thermal reaction be 160~200 DEG C at heating reaction 12~for 24 hours.
7. the preparation side of redox graphene according to claim 1 or 2/stannate anode material of lithium-ion battery
Method, which is characterized in that the high-temperature calcination temperature is 300~550 DEG C, and calcination atmosphere is nitrogen atmosphere, calcination time is 3~
4h。
8. negative using redox graphene/stannate sodium-ion battery that the method as described in claim 1~7 is prepared
Pole material.
9. the application of redox graphene as claimed in claim 8/stannate anode material of lithium-ion battery, feature exist
In after mixing by the redox graphene/stannate anode material of lithium-ion battery and binder and conductive agent
Coated on copper foil, sodium-ion battery negative plate is obtained after drying, roll-in.
10. the application of redox graphene according to claim 9/stannate anode material of lithium-ion battery, special
Sign is：
The redox graphene/stannate anode material of lithium-ion battery, binder and conductive agent weight ratio be (70~
80):(20~10):10；
The binder is sodium carboxymethylcellulose；
The conductive agent is conductive carbon Super-P or conductive black；
The drying condition be 50~120 DEG C at vacuum drying 5~for 24 hours；
The thickness of the coating is 100~180 μm, and the overall thickness of the electrode slice roll-in is 75~150 μm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111135837A (en) * | 2019-12-18 | 2020-05-12 | 常州大学 | Persulfate activator and preparation method and application thereof |
| CN111261857A (en) * | 2020-01-21 | 2020-06-09 | 南京航空航天大学 | FePS for sodium ion battery3/NC composite negative electrode material, preparation method thereof and sodium ion battery |
| CN113697847A (en) * | 2021-08-05 | 2021-11-26 | 湖北工程学院 | ZnSnO3Preparation method of nanorod/RGO composite material and energy storage application thereof |
| CN114023942A (en) * | 2021-11-09 | 2022-02-08 | 赣南科技学院 | Reduced graphene oxide loaded FeTe composite material and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102760885A (en) * | 2012-07-23 | 2012-10-31 | 浙江大学 | Tin-base complex oxide/graphene composite material, and preparation method and application thereof |
| CN102916187A (en) * | 2012-11-06 | 2013-02-06 | 西北工业大学 | Method for preparing graphene/lithium stannate composite material of lithium battery |
| CN103972497A (en) * | 2014-05-27 | 2014-08-06 | 华南师范大学 | Co2SnO4/C nano-composite negative electrode material for lithium ion battery, preparation and application of Co2SnO4/C nano-composite negative electrode material |
| CN105449177A (en) * | 2015-11-30 | 2016-03-30 | 中南大学 | Porous cubic ZnSO3@graphene negative electrode material used for sodium ion battery and preparation method for porous cubic ZnSO3@graphene negative electrode material |
| CN107224978A (en) * | 2017-07-24 | 2017-10-03 | 福州大学 | The preparation method and applications of hydroxyl stannate cobalt/graphene composite photocatalyst |
| CN107275006A (en) * | 2017-06-29 | 2017-10-20 | 哈尔滨理工大学 | Redox graphene/SnO2Compound transparent electricity conductive film and preparation method thereof |
| CN107799748A (en) * | 2017-10-23 | 2018-03-13 | 天津师范大学 | A kind of nanoscale cube cobaltous stannate and graphene composite material and preparation method and application |
-
2018
- 2018-07-27 CN CN201810842705.6A patent/CN108807945A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102760885A (en) * | 2012-07-23 | 2012-10-31 | 浙江大学 | Tin-base complex oxide/graphene composite material, and preparation method and application thereof |
| CN102916187A (en) * | 2012-11-06 | 2013-02-06 | 西北工业大学 | Method for preparing graphene/lithium stannate composite material of lithium battery |
| CN103972497A (en) * | 2014-05-27 | 2014-08-06 | 华南师范大学 | Co2SnO4/C nano-composite negative electrode material for lithium ion battery, preparation and application of Co2SnO4/C nano-composite negative electrode material |
| CN105449177A (en) * | 2015-11-30 | 2016-03-30 | 中南大学 | Porous cubic ZnSO3@graphene negative electrode material used for sodium ion battery and preparation method for porous cubic ZnSO3@graphene negative electrode material |
| CN107275006A (en) * | 2017-06-29 | 2017-10-20 | 哈尔滨理工大学 | Redox graphene/SnO2Compound transparent electricity conductive film and preparation method thereof |
| CN107224978A (en) * | 2017-07-24 | 2017-10-03 | 福州大学 | The preparation method and applications of hydroxyl stannate cobalt/graphene composite photocatalyst |
| CN107799748A (en) * | 2017-10-23 | 2018-03-13 | 天津师范大学 | A kind of nanoscale cube cobaltous stannate and graphene composite material and preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| PENG LIU等: ""Hollow Amorphous MnSnO3 Nanohybrid with Nitrogen-Doped"", 《ELECTROCHIMICA ACTA》 * |
| YANKUNWANG等: ""Fabrication of novel rugby like ZnSnO3/reduced graphene oxide composites as a high performance anode material for lithium ion batteries"", 《MATERIALSLETTERS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111135837A (en) * | 2019-12-18 | 2020-05-12 | 常州大学 | Persulfate activator and preparation method and application thereof |
| CN111135837B (en) * | 2019-12-18 | 2022-12-06 | 常州大学 | Persulfate activator and preparation method and application thereof |
| CN111261857A (en) * | 2020-01-21 | 2020-06-09 | 南京航空航天大学 | FePS for sodium ion battery3/NC composite negative electrode material, preparation method thereof and sodium ion battery |
| CN111261857B (en) * | 2020-01-21 | 2022-04-29 | 南京航空航天大学 | FePS for sodium ion battery3/NC composite negative electrode material, preparation method thereof and sodium ion battery |
| CN113697847A (en) * | 2021-08-05 | 2021-11-26 | 湖北工程学院 | ZnSnO3Preparation method of nanorod/RGO composite material and energy storage application thereof |
| CN113697847B (en) * | 2021-08-05 | 2022-04-01 | 湖北工程学院 | ZnSnO3Preparation method of nanorod/RGO composite material and energy storage application thereof |
| CN114023942A (en) * | 2021-11-09 | 2022-02-08 | 赣南科技学院 | Reduced graphene oxide loaded FeTe composite material and preparation method and application thereof |
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