CN109830649A - A kind of preparation process of long circulation life, height ratio capacity flexible electrode - Google Patents
A kind of preparation process of long circulation life, height ratio capacity flexible electrode Download PDFInfo
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- CN109830649A CN109830649A CN201910033360.4A CN201910033360A CN109830649A CN 109830649 A CN109830649 A CN 109830649A CN 201910033360 A CN201910033360 A CN 201910033360A CN 109830649 A CN109830649 A CN 109830649A
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- walled carbon
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Abstract
The present invention relates to the preparation process of a kind of long circulation life, height ratio capacity flexible electrode, include the following steps: the acid processing of (1) multi-walled carbon nanotube；(2) it the preparation of electrode: disperses manganese source and mixing through step (1) treated multi-walled carbon nanotube by predetermined ratio in solution, by electrostatic interaction the manganese ion in manganese source is adsorbed on multi-walled carbon nanotube in predetermined temperature, then carbonate solution is added, react the manganese carbonate of predetermined time generation anchoring on multi-walled carbon nanotubes, it is filtered by vacuum again, dries to form fexible film, finally the sustained response predetermined time makes manganese carbonate be decomposed to form manganese oxide under predetermined temperature and atmosphere of inert gases by fexible film.Preparation method is simple by the present invention, raw materials used cheap, and the product flexibility prepared is good, activity substance content is high, shows long circulation life and height ratio capacity when as lithium battery flexibility cathode.
Description
Technical field
The invention belongs to electrode material preparation technical fields, and in particular to a kind of long circulation life, height ratio capacity flexible electrical
The preparation process of pole.
Background technique
With the progress and development of human society, demand of the people to lithium ion battery is more and more, simultaneously to lithium
The requirement of ion battery is also higher and higher.The especially exploitation of new-energy automobile needs lithium ion battery to have high energy close
Degree and long cycle life, while nowadays intelligent wearable device needs lithium ion battery to have flexibility, and these requirements are very
Electrode material is depended in big degree.The lithium ion battery negative material of commercial applications is mainly graphite at present, but graphite material
Expect that theoretical specific capacity is low and flexibility is poor, the application for being unable to satisfy long circulation life high-energy density flexible lithium ion battery needs
It asks.Therefore the positive and negative anodes electrode material that research specific capacity is high, flexibility is good has free-revving engine and meaning.However, the prior art
In, long circulation life high-energy density flexible electrode preparation method complexity is cumbersome, with high costs；And preparation electrode flexibility compared with
Difference, cycle life are still shorter, and energy density is lower.
Therefore develop it is a kind of preparation method is simple, it is used low in cost, it is environmental-friendly, and the electrode prepared as lithium from
Preparation process when sub- battery cathode with long circulation life and height ratio capacity.
Summary of the invention
It is low in cost it is an object of the present invention to provide a kind of simple for process, and the electrode prepared is as lithium ion battery
Preparation process when cathode with long circulation life and height ratio capacity.
Above-mentioned purpose is to be achieved through the following technical solutions: a kind of preparation of long circulation life, height ratio capacity flexible electrode
Technique includes the following steps:
(1) the acid processing of multi-walled carbon nanotube；
(2) preparation of long circulation life, height ratio capacity flexible electrode: by manganese source and through step (1) treated multi wall carbon
Nanotube is scattered in solution by predetermined ratio mixing, makes the manganese ion in manganese source be adsorbed onto multi wall by electrostatic interaction
In carbon nanotube, carbonate solution is then added, 2~6h is reacted at 0 DEG C and generates the carbonic acid of anchoring on multi-walled carbon nanotubes
Manganese quantum dot, then be filtered by vacuum, dry to form fexible film, finally by fexible film in 550~700 DEG C and inert gas
2~4h of sustained response predetermined time makes manganese carbonate quantum dot be decomposed to form manganese oxide quantum dot under atmosphere, wherein the multi wall
The mass ratio of carbon nanotube and manganese oxide quantum dot is 4:4~10.
Main composition material in flexible electrode prepared by the present invention is multi-walled carbon nanotube and manganese oxide quantum dot.This hair
Bright using multi-walled carbon nanotube is raw material as flexible self-supporting body and collector, utilizes its strong mechanical flexibility and good
Electric conductivity, by being mixed after simply pre-processing with manganese source, since multi-walled carbon nanotube has hydroxyl group after peracid treatment
And it is negatively charged, and manganese ion is positively charged, after stirring by mixing, due to the two one positively charged one it is negatively charged, so
Under electrostatic interaction, so that manganese ion is adsorbed on multi-walled carbon nanotube, at 0 DEG C, the addition of carbonate solution, so that
Manganese ion and carbonate react, and react slow under above-mentioned condition, so that formation manganese carbonate is smaller after reaction, is filtered by vacuum, is dried
The anchoring of manganese oxide quantum dot has been decomposed to form after annealing on multi-walled carbon nanotubes, it is verified, due to manganese oxide quantum dot
Diameter between 3-5nm, therefore have very big specific surface area, thus increase more active sites, stock utilization and
The cushion space of volume expansion, results in long circulation life and height ratio capacity.
Manganese oxide quantum dot is anchored on multi wall using the method for electrostatic self-assembled, vacuum filtration and annealing by the present invention
In carbon nanotube, obtain having large specific surface area, stock utilization high and the flexible electrode of good toughness；Present invention process preparation side
Method is simple and easy, low in cost, long circulation life, the height ratio capacity flexible electrode of preparation, due to the introducing of multi-walled carbon nanotube
And enhance mechanical flexibility and conductivity of composite material；Simultaneous oxidation manganese quantum dot size is small, large specific surface area, active site
It is more, to have more high usage and more volume expansion cushion spaces, and then improve the performance of electrode material.
Further technical solution is, in the step (2), manganese source is six hydrated manganese sulfates, in manganese nitrate, manganese chloride
It is one or more.It is preferred that the manganese source is six hydrated manganese sulfates.
Further technical solution is that in the step (2), carbonate is ammonium hydrogen carbonate.Experiment proves that under this condition
The manganese oxide quantum dot ultimately produced is manganese monoxide quantum dot.
Further technical solution is, in the step (2), the ratio of control multi-walled carbon nanotube and manganese source makes described
The mass ratio of multi-walled carbon nanotube and manganese oxide quantum dot is 4:4~10 in long circulation life height ratio capacity flexible electrode；It is preferred that
The mass ratio of multi-walled carbon nanotube described in the long circulation life height ratio capacity flexible electrode and manganese oxide quantum dot is 4:
8.2。
Further technical solution is that the reaction time after carbonate solution is added in step (2) is 3h, and fexible film exists
600 DEG C of sustained response 3h.
Further technical solution is the cleaning for further including multi-walled carbon nanotube after acidification in the step (1), dry
It is dry.
Further technical solution is, the acid source of acidification carbon nanotube is the concentrated sulfuric acid, concentrated hydrochloric acid and dense in the step (1)
One of nitric acid is a variety of.
Further technical solution is that the acid source is concentrated nitric acid, and concentrated nitric acid amount is 3~12ml in the step (1).It is excellent
Choosing, the acidification concentrated nitric acid amount are 5ml.
Further technical solution is that the inert gas is nitrogen or argon gas.Preferably argon gas.
Further technical solution is that the carbon nanotube diameter is 18~28nm.Preferably 20nm.
Further technical solution is that the drying in the step (2) is vacuum freeze drying, vacuum high-temperature is dry, often
One of warm air drying is a variety of.Preferably vacuum freeze drying.
Compared with the prior art, the electrode of present invention process preparation, active material is smaller to reach 3-5nm, simultaneously
With higher specific surface area, more active sites and shorter ion transport distance, to have good electrochemistry
Store up lithium performance.After tested, specific surface area is up to 104.2m2g-1, electrode is flexible and keeps integrality；The experimental results showed that
When the electrode for using it to prepare is as negative electrode of lithium ion battery, there is the cycle life of length, recycled under 1A/g current density
Capacity retention ratio is up to 133% after 1000 times；There is high specific capacity simultaneously, after being recycled 1000 times under 1A/g current density,
Specific discharge capacity is up to 883.3mAh/g.Preparation method of the present invention is low in cost, simple for process, the electrode cycle longevity of preparation
It is high to order long specific capacity.
Detailed description of the invention
It constitutes a part of attached drawing of the invention to be used to provide further understanding of the present invention, schematic implementation of the invention
Example and its explanation are used to explain the present invention, and are not constituted improper limitations of the present invention.
Fig. 1 be the embodiment of the present invention 1 prepare long circulation life, height ratio capacity flexible electrode XRD diagram, wherein
Illustration is to follow using the electrode as 1000 vice-minister in the case where current density is 1A/g, are carried out when cathode of lithium battery in Fig. 1
Ring test result figure；
Fig. 2 is long circulation life height ratio capacity flexible electrode crooked test figure prepared by the embodiment of the present invention 1；
Figure a in Fig. 3 is long circulation life height ratio capacity flexible electrode SEM figure prepared by the embodiment of the present invention 1,
Scheming b is long circulation life, height ratio capacity flexible electrode TEM figure prepared by the embodiment of the present invention 1；
Fig. 4 is the BET adsorption curve of the long circulation life of the preparation of the embodiment of the present invention 1, height ratio capacity flexible electrode, wherein
Illustration in Fig. 3 is the graph of pore diameter distribution of the electrode；
Fig. 5 is the TGA figure of the long circulation life of the preparation of the embodiment of the present invention 1, height ratio capacity flexible electrode；
Figure a in Fig. 6 is the long circulation life of the preparation of the embodiment of the present invention 1, height ratio capacity flexible electrode as lithium battery
Cyclic voltammetry curve when negative electrode material；Figure b and figure c is respectively the flexible electrode of the preparation of the embodiment of the present invention 1 as lithium battery
Charging and discharging curve and multiplying power figure when negative electrode material under 0.2A/g current density；Scheming d is flexibility prepared by the embodiment of the present invention 1
Recycling figure of the electrode under 0.2A/g current density.
Specific embodiment
Present invention will now be described in detail with reference to the accompanying drawings., the description of this part be only it is exemplary and explanatory, do not answer
There is any restriction effect to protection scope of the present invention.In addition, description of the those skilled in the art according to this document, it can be right
Feature in this document in embodiment and in different embodiments carries out the corresponding combination.
Embodiment 1
It weighs commercialization 300mg multi-walled carbon nanotube and is put into sand core, sand core and 5ml concentrated nitric acid are put into reaction kettle and are packed into
Iron-clad, is then transferred into 200 DEG C of 2h acidifications in hydro-thermal furnace, and the multi-walled carbon nanotube after acidification is cleaned and dried.Claim
Six hydrated manganese sulfates of the multi-walled carbon nanotube and 1mmol that take 40mg acid to handle well are put into beaker, and 50ml water is added and is stirred
The broken ultrasound of breading is allowed to fully dispersed and after stirring 1h, the ammonium hydrogencarbonate of 3mmol uniformly is added, and continues to stir 3h at 0 DEG C, then
Vacuum filtration and vacuum freeze drying processing are carried out, the flexible membrane of acquisition is put into tube furnace and is annealed in 600 DEG C of argon gas 3h, shape
At manganese oxide quantum dot and multi-walled carbon nanotube flexible compound electrode.
The specific nature of product: it has been determined that manganese oxide and multi-walled carbon nanotube flexible electrode contain by XRD characterization and illustration
Manganese oxide and carbon material and have long circulation life and height ratio capacity；By crooked test determined preparation electrode have compared with
Good flexibility；The anchoring of manganese oxide quantum dot is determined on multi-walled carbon nanotubes by SEM and TEM characterization, and manganese oxide amount
For sub- spot diameter in 3-5nm, the distribution of simultaneous oxidation manganese quantum dot is relatively uniform not to have agglomeration；Pass through specific surface area measuring and calculation
Obtaining specific surface area is 104.2m2g-1；It tests to obtain oxidation manganese content to be 67.4% by thermogravimetric analysis.
Through electrochemical property test, the manganese oxide quantum dot and multi-walled carbon nanotube flexible electrode of preparation are as lithium-ion electric
Data illustrate best when the cathode of pond.
As shown in Figure 1, the position at manganese oxide quantum dot and multi-walled carbon nanotube flexible electrode material peak and manganese oxide standard
Card can correspond, and thus illustrate the material manganese oxide of preparation, and 25.7.Corresponding peak is multi-walled carbon nanotube
Peak.Illustration in Fig. 1 has recycled 4 times in the case where current density is 0.1A/g first it is found that when the electrode is as cathode of lithium battery, this
It is specific discharge capacity for better activated material, after the 5th circulation is 647.2mAh/g, then under 1A/g current density
It has recycled 1000 times, it can be observed that first be steadily then gradually increasing of specific discharge capacity is tended to be steady again, this leads preceding 200 circulations
Further to be activated from material and bivalent manganese to value Mn oxidation lead to more multielectron transfer caused by, when circulation 1000 times
Afterwards, specific discharge capacity is up to 883.3mAh/g, and specific capacity conservation rate is up to 136%, and showing the electrode has long circulation
Service life and high specific capacity.
As shown in Figure 2, manganese oxide quantum dot and multi-walled carbon nanotube flexible electrode are still complete by crooked test, explanation
The electrode has preferable flexibility.
Manganese oxide and multi-walled carbon nanotube dispersion are especially uniform known to the figure a in Fig. 3, have not a particle of reunion；Scheming can in b
It becomes apparent from and finds out the anchoring of manganese oxide quantum dot on the carbon nanotubes, diameter does not have agglomeration in 3-5nm.
By Fig. 4 it can be concluded that manganese oxide and multi-walled carbon nanotube flexible electrode have high specific surface area 104.2m2g-1, figure
Illustration can be seen that flexible electrode aperture is distributed mainly on micropore in 4.
Manganese content is aoxidized in this material as shown in Figure 5 is up to 67.4%.
A pair of of redox peaks, and second of big, explanation of area ratio that third time surrounds can be seen that by the figure a of Fig. 6
The electrode material is gradually activating；Figure b and figure d is respectively manganese oxide quantum dot and multi-walled carbon nanotube flexible electrode as lithium electricity
Charging and discharging curve and circulation when the negative electrode material of pond at 0.1A/g may determine that manganese oxide by charging and discharging curve and circulation figure
The cyclical stability and high specific capacity that quantum dot and carbon nano tube flexible electrode have had；D is schemed it is found that in high current density
Under 3.2A/g, this electrode still has very high specific capacity, thus illustrates manganese oxide quantum dot and multi-walled carbon nanotube flexible electrical
It is great to have brilliant high rate performance.
Embodiment 2
It weighs commercialization 300mg multi-walled carbon nanotube and is put into sand core, sand core and 5ml concentrated nitric acid are put into reaction kettle and are packed into
Iron-clad, is then transferred into 200 DEG C of 2h acidifications in hydro-thermal furnace, and the multi-walled carbon nanotube after acidification is cleaned and dried.Claim
Six hydrated manganese sulfates of the multi-walled carbon nanotube and 1mmol that take 40mg acid to handle well are put into beaker, and 50ml water is added and is stirred
The broken ultrasound of breading is allowed to fully dispersed and uniformly after stirring 1h, by the ammonium hydrogencarbonate addition of 3mmol, continues to stir 3h at 0 DEG C,
Vacuum filtration and vacuum freeze drying processing are then carried out, the flexible membrane of acquisition is put into tube furnace in 700 DEG C of argon gas and is annealed
4h forms manganese oxide quantum dot and multi-walled carbon nanotube flexible compound electrode.
The specific nature of product: it has been determined that manganese oxide and multi-walled carbon nanotube flexible electrode contain by XRD characterization and illustration
Manganese oxide and carbon material and have long circulation life and height ratio capacity；By crooked test, flexibility is general；By SEM and
TEM characterization has determined the anchoring of manganese oxide quantum dot on multi-walled carbon nanotubes, and manganese oxide lateral size of dots is in 4-8nm, simultaneously
The distribution of manganese oxide quantum dot is relatively uniform not to have agglomeration；Obtaining specific surface area by specific surface area measuring and calculation is
94.2m2g-1；It tests to obtain oxidation manganese content to be 65.4% by thermogravimetric analysis.
Embodiment 3
It weighs commercialization 300mg multi-walled carbon nanotube and is put into sand core, sand core and 5ml concentrated nitric acid are put into reaction kettle and are packed into
Iron-clad, is then transferred into 200 DEG C of 2h acidifications in hydro-thermal furnace, and the multi-walled carbon nanotube after acidification is cleaned and dried.Claim
Six hydrated manganese sulfates of the multi-walled carbon nanotube and 1mmol that take 40mg acid to handle well are put into beaker, and 50ml water is added and is stirred
The broken ultrasound of breading is allowed to fully dispersed and uniformly after stirring 1h, by the ammonium hydrogencarbonate addition of 3mmol, continues to stir 4h at 0 DEG C,
Vacuum filtration and vacuum freeze drying processing are then carried out, the flexible membrane of acquisition is put into tube furnace in 600 DEG C of argon gas and is annealed
3h forms manganese oxide quantum dot and multi-walled carbon nanotube flexible compound electrode.
The specific nature of product: it has been determined that manganese oxide and multi-walled carbon nanotube flexible electrode contain by XRD characterization and illustration
Manganese oxide and carbon material and have long circulation life and height ratio capacity；By crooked test determined preparation electrode have compared with
Good flexibility；The anchoring of manganese oxide quantum dot is determined on multi-walled carbon nanotubes by SEM and TEM characterization, and manganese oxide amount
For sub- spot diameter in 4-7nm, the distribution of simultaneous oxidation manganese quantum dot is relatively uniform not to have agglomeration；Pass through specific surface area measuring and calculation
Obtaining specific surface area is 101.2m2g-1；It tests to obtain oxidation manganese content to be 68.8% by thermogravimetric analysis.
Embodiment 4
It weighs commercialization 300mg multi-walled carbon nanotube and is put into sand core, sand core and 4ml concentrated nitric acid are put into reaction kettle and are packed into
Iron-clad, is then transferred into 200 DEG C of 2h acidifications in hydro-thermal furnace, and the multi-walled carbon nanotube after acidification is cleaned and dried.Claim
Six hydrated manganese sulfates of the multi-walled carbon nanotube and 1mmol that take 40mg acid to handle well are put into beaker, and 50ml water is added and is stirred
The broken ultrasound of breading is allowed to fully dispersed and uniformly after stirring 1h, by the ammonium hydrogencarbonate addition of 3mmol, continues to stir 2h at 0 DEG C,
Vacuum filtration and vacuum freeze drying processing are then carried out, the flexible membrane of acquisition is put into tube furnace in 550 DEG C of argon gas and is annealed
4h forms manganese oxide quantum dot and multi-walled carbon nanotube flexible compound electrode.
The specific nature of product: it has been determined that manganese oxide and multi-walled carbon nanotube flexible electrode contain by XRD characterization and illustration
Manganese oxide and carbon material and have long circulation life and height ratio capacity；By crooked test determined preparation electrode have compared with
Good flexibility；The anchoring of manganese oxide quantum dot is determined on multi-walled carbon nanotubes by SEM and TEM characterization, and manganese oxide amount
For sub- spot diameter in 4-8nm, the distribution of simultaneous oxidation manganese quantum dot is relatively uniform not to have agglomeration；Pass through specific surface area measuring and calculation
Obtaining specific surface area is 98.2m2g-1；It tests to obtain oxidation manganese content to be 65.4% by thermogravimetric analysis.
Embodiment 5
It weighs commercialization 300mg multi-walled carbon nanotube and is put into sand core, sand core and 5ml concentrated nitric acid are put into reaction kettle and are packed into
Iron-clad, is then transferred into 200 DEG C of 2h acidifications in hydro-thermal furnace, and the multi-walled carbon nanotube after acidification is cleaned and dried.Claim
Six hydrated manganese sulfates of the multi-walled carbon nanotube and 1mmol that take 60mg acid to handle well are put into beaker, and 50ml water is added and is stirred
The broken ultrasound of breading is allowed to fully dispersed and uniformly after stirring 1h, by the ammonium hydrogencarbonate addition of 3mmol, continues to stir 6h at 0 DEG C,
Vacuum filtration and vacuum freeze drying processing are then carried out, the flexible membrane of acquisition is put into tube furnace in 600 DEG C of argon gas and is annealed
2h forms manganese oxide quantum dot and multi-walled carbon nanotube flexible compound electrode.
The specific nature of product: it has been determined that manganese oxide and multi-walled carbon nanotube flexible electrode contain by XRD characterization and illustration
Manganese oxide and carbon material and have long circulation life and height ratio capacity；It has been determined that the electrode of preparation has very by crooked test
Good flexibility；The anchoring of manganese oxide quantum dot is determined on multi-walled carbon nanotubes by SEM and TEM characterization, and manganese oxide amount
For sub- spot diameter in 5-9nm, the distribution of simultaneous oxidation manganese quantum dot is relatively uniform not to have agglomeration；Pass through specific surface area measuring and calculation
Obtaining specific surface area is 88.2m2g-1；It tests to obtain oxidation manganese content to be 55.4% by thermogravimetric analysis.
Embodiment 6
It weighs commercialization 300mg multi-walled carbon nanotube and is put into sand core, sand core and 5ml concentrated nitric acid are put into reaction kettle and are packed into
Iron-clad, is then transferred into 200 DEG C of 2h acidifications in hydro-thermal furnace, and the multi-walled carbon nanotube after acidification is cleaned and dried.Claim
Six hydrated manganese sulfates of the multi-walled carbon nanotube and 1mmol that take 80mg acid to handle well are put into beaker, and 50ml water is added and is stirred
The broken ultrasound of breading is allowed to fully dispersed and uniformly after stirring 1h, by the ammonium hydrogencarbonate addition of 2mmol, continues to stir 3h at 0 DEG C,
Vacuum filtration and vacuum freeze drying processing are then carried out, the flexible membrane of acquisition is put into tube furnace in 600 DEG C of argon gas and is annealed
3h forms manganese oxide quantum dot and multi-walled carbon nanotube flexible compound electrode.
The specific nature of product: it has been determined that manganese oxide and multi-walled carbon nanotube flexible electrode contain by XRD characterization and illustration
Manganese oxide and carbon material and have long circulation life and height ratio capacity；It has been determined that the electrode of preparation has spy by crooked test
Good flexibility；The anchoring of manganese oxide quantum dot is determined on multi-walled carbon nanotubes by SEM and TEM characterization, and manganese oxide amount
For sub- spot diameter in 4-6nm, the distribution of simultaneous oxidation manganese quantum dot is relatively uniform not to have agglomeration；Pass through specific surface area measuring and calculation
Obtaining specific surface area is 70.5m2g-1；It tests to obtain oxidation manganese content to be 46.4% by thermogravimetric analysis.
Embodiment 7
It weighs commercialization 300mg multi-walled carbon nanotube and is put into sand core, sand core and 5ml concentrated nitric acid are put into reaction kettle and are packed into
Iron-clad, is then transferred into 200 DEG C of 2h acidifications in hydro-thermal furnace, and the multi-walled carbon nanotube after acidification is cleaned and dried.Claim
Six hydrated manganese sulfates of the multi-walled carbon nanotube and 1.5mmol that take 40mg acid to handle well are put into beaker, and 50ml water is added and carries out
Stirring crushes ultrasound and is allowed to fully dispersed uniform, and after stirring 1h, the sodium carbonate of 5mmol is added, and continues to stir 3h at 0 DEG C, then
Vacuum filtration and vacuum freeze drying processing are carried out, the flexible membrane of acquisition is put into tube furnace and is annealed in 600 DEG C of argon gas 3h, shape
At manganese oxide quantum dot and multi-walled carbon nanotube flexible compound electrode.
The specific nature of product: manganese oxide and multi-walled carbon nanotube flexible electrode manganese oxide have been determined by XRD characterization
And carbon material；It has been determined that the electrode flexibility of preparation is very poor by crooked test；Manganese oxide has been determined by SEM and TEM characterization
It is anchored on multi-walled carbon nanotubes, and manganese oxide diameter, in 10-25nm, simultaneous oxidation manganese is unevenly distributed, and agglomeration is serious,
It is not manganese oxide quantum dot.Obtaining specific surface area by specific surface area measuring and calculation is 40.5m2g-1；It is surveyed by thermogravimetric analysis
It is 75.4% that examination, which obtains oxidation manganese content,.
Embodiment 8
It weighs commercialization 300mg multi-walled carbon nanotube and is put into sand core, sand core and 5ml concentrated nitric acid are put into reaction kettle and are packed into
Iron-clad, is then transferred into 200 DEG C of 2h acidifications in hydro-thermal furnace, and the multi-walled carbon nanotube after acidification is cleaned and dried.Claim
Six hydrated manganese sulfates of the multi-walled carbon nanotube and 0.6mmol that take 40mg acid to handle well are put into beaker, and 50ml water is added and carries out
Stirring crushes ultrasound and is allowed to fully dispersed uniform, and after stirring 1h, the sodium carbonate of 2mmol is added, and continues to stir 3h at 0 DEG C, then
Vacuum filtration and vacuum freeze drying processing are carried out, the flexible membrane of acquisition is put into tube furnace and is annealed in 600 DEG C of argon gas 3h, shape
At manganese oxide quantum dot and multi-walled carbon nanotube flexible compound electrode.
The specific nature of product: manganese oxide and multi-walled carbon nanotube flexible electrode manganese oxide have been determined by XRD characterization
And carbon material；It has been determined that the electrode flexibility of preparation is fine by crooked test；Manganese oxide has been determined by SEM and TEM characterization
It is anchored on multi-walled carbon nanotubes, simultaneous oxidation manganese distribution uniform, but is not manganese oxide quantum dot.It is tested by specific surface area
It is 100.5m that specific surface area, which is calculated,2g-1；It tests to obtain oxidation manganese content to be 51.4% by thermogravimetric analysis.
Choose other other carbonate, such as ammonium carbonates, sodium bicarbonate in addition to ammonium hydrogen carbonate the experiment has found that product
Manganese oxide is not manganese oxide quantum dot.The above multi-wall carbon nano-tube pipe diameter is 18~28nm, preferably 20nm.
Manganese oxide quantum dot and carbon nano tube flexible electrode characterization
The structure and morphology characterization of manganese oxide quantum dot and carbon nano tube flexible electrode pass through Ragaku D type (Rigaku
Produce) X-ray diffractometer (X-ray Diffractometer, XRD), model JEOLJEM-2100 (Japan Electronics strain formula meeting
Society) transmission electron microscope (Transmission Electron Microscope, TEM) and S4800 type scanning electron microscope
(scanning electron micro-scope, SEM).N2(Micromeritics TriStar II 3020) is adsorbed to survey
Examination；Specific surface area uses Barrett- according to Brunauer-Emmett-Teller (BET) theoretical calculation, pore-size distribution (PSD)
Joyner-Halenda (BJH) model calculates；It aoxidizes manganese content and passes through model NETZSCH TG 209F1Libra thermogravimetric analyzer
It is analyzed.
Manganese oxide quantum dot and multi-walled carbon nanotube flexible electrode battery assembly and electrochemical property test
By manganese oxide quantum dot and multi-walled carbon nanotube flexible electrode be cut into quality be 0.8-1.5mg disk directly as
Working electrode, metal lithium sheet are to electrode, 1mol/L LiPF6- EC/DMC/EMC (1: 1: 1) is electrolyte, polypropylene
Celgard 2325 makees diaphragm and is assembled into 2025 type buttons, half electricity in the glove box of argon atmosphere and water content less than 1 μ L/L
Pond.Constant current charge-discharge test (GCD) is carried out on new prestige battery test system, and test voltage range is 0.01~3.00V.It follows
Ring volt-ampere (CV) test and AC impedance (EIS) test are carried out on occasion China CHI660 type electrochemical workstation.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (8)
1. the preparation process of a kind of long circulation life, height ratio capacity flexible electrode, which comprises the steps of:
(1) the acid processing of multi-walled carbon nanotube；
(2) preparation of long circulation life height ratio capacity flexible electrode: by manganese source and through step (1) treated multi-walled carbon nanotube
It is scattered in solution by predetermined ratio mixing, makes the manganese ion in manganese source be adsorbed onto multi-wall carbon nano-tube by electrostatic interaction
Then carbonate solution is added in Guan Shang, 2~6h is reacted at 0 DEG C and generates the manganese carbonate quantum of anchoring on multi-walled carbon nanotubes
Point, then be filtered by vacuum, dry to form fexible film, finally by fexible film under 550~700 DEG C and atmosphere of inert gases
Sustained response 2~4h predetermined time makes manganese carbonate quantum dot be decomposed to form manganese oxide quantum dot, wherein the multi-wall carbon nano-tube
The mass ratio of pipe and manganese oxide quantum dot is 4:4~10.
2. the preparation process of long circulation life according to claim 1, height ratio capacity flexible electrode, which is characterized in that institute
The manganese source that uses in step (2) is stated as one of six hydrated manganese sulfates, manganese nitrate, manganese chloride or a variety of.
3. the preparation process of long circulation life according to claim 1, height ratio capacity flexible electrode, which is characterized in that institute
The carbonate used in step (2) is stated as ammonium hydrogencarbonate.
4. the preparation process of long circulation life according to claim 1, height ratio capacity flexible electrode, which is characterized in that institute
State further include in step (1) acid treated carbon nanotube cleaning, drying.
5. the preparation process of long circulation life according to claim 5, height ratio capacity flexible electrode, which is characterized in that institute
Stating acid source in acid processing is concentrated nitric acid, and concentrated nitric acid amount is 3~12ml in the step (1).
6. the preparation process of long circulation life according to claim 5, height ratio capacity flexible electrode, which is characterized in that institute
Stating inert gas is ordinary nitrogen or common argon gas.
7. the preparation process of long circulation life according to claim 5, height ratio capacity flexible electrode, which is characterized in that institute
Stating multi-wall carbon nano-tube pipe diameter is 18~28nm.
8. the preparation process of long circulation life according to claim 1, height ratio capacity flexible electrode, which is characterized in that institute
It is one of dry or a variety of in vacuum freeze drying, vacuum high-temperature drying, normal temperature air for stating the drying in step (2).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114560448A (en) * | 2022-02-23 | 2022-05-31 | 西安交通大学 | Preparation method and application of manganese selenide nano material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1953935A (en) * | 2004-05-14 | 2007-04-25 | 索尼德国有限责任公司 | Composite materials comprising carbon nanotubes and metal carbonates |
| CN103762366A (en) * | 2013-11-25 | 2014-04-30 | 国家电网公司 | Preparation method of carbon nanotube composite electrode |
| CN103972518A (en) * | 2013-02-05 | 2014-08-06 | 中国科学院大连化学物理研究所 | Manganese dioxide/carbon nanocomposite, and preparation method and application thereof |
| CN107946084A (en) * | 2017-10-26 | 2018-04-20 | 广东工业大学 | A kind of metal oxide/three-dimensional porous graphene composite material and its preparation method and application |
| CN108172409A (en) * | 2018-01-10 | 2018-06-15 | 西北师范大学 | A kind of preparation method of three-dimensional flower-shaped structure graphite alkene quantum dot/manganous hydroxide composite material |
| US20180269442A1 (en) * | 2017-03-20 | 2018-09-20 | Bing R. Hsieh | Printed planar lithium-ion batteries |
-
2019
- 2019-01-14 CN CN201910033360.4A patent/CN109830649B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1953935A (en) * | 2004-05-14 | 2007-04-25 | 索尼德国有限责任公司 | Composite materials comprising carbon nanotubes and metal carbonates |
| CN103972518A (en) * | 2013-02-05 | 2014-08-06 | 中国科学院大连化学物理研究所 | Manganese dioxide/carbon nanocomposite, and preparation method and application thereof |
| CN103762366A (en) * | 2013-11-25 | 2014-04-30 | 国家电网公司 | Preparation method of carbon nanotube composite electrode |
| US20180269442A1 (en) * | 2017-03-20 | 2018-09-20 | Bing R. Hsieh | Printed planar lithium-ion batteries |
| CN107946084A (en) * | 2017-10-26 | 2018-04-20 | 广东工业大学 | A kind of metal oxide/three-dimensional porous graphene composite material and its preparation method and application |
| CN108172409A (en) * | 2018-01-10 | 2018-06-15 | 西北师范大学 | A kind of preparation method of three-dimensional flower-shaped structure graphite alkene quantum dot/manganous hydroxide composite material |
Non-Patent Citations (3)
| Title |
|---|
| HUANXIN LI等: "Ultra-fast transfer and high storage of Li+/Na+ in MnO quantum dots@carbon hetero-nanotubes: Appropriate quantum dots to improve the rate", 《ENERGY STORAGE MATERIALS》 * |
| XIAOFEI SUN等: "The composite sphere of manganese oxide and carbon nanotubes as a prospective anode material for lithium-ion batteries", 《JOURNAL OF POWER SOURCES》 * |
| XIONG LIU等: "Free-standing Hierarchical Porous Assemblies of Commercial TiO2 Nanocrystals and Multi-walled Carbon Nanotubes as High-performance Anode Materials for Sodium Ion Batteries", 《ELECTROCHIMICA ACTA》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114560448A (en) * | 2022-02-23 | 2022-05-31 | 西安交通大学 | Preparation method and application of manganese selenide nano material |
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