CN109888233A - It is a kind of can charge and discharge Grazing condition kalium ion battery, preparation method and application - Google Patents
It is a kind of can charge and discharge Grazing condition kalium ion battery, preparation method and application Download PDFInfo
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- CN109888233A CN109888233A CN201910167560.9A CN201910167560A CN109888233A CN 109888233 A CN109888233 A CN 109888233A CN 201910167560 A CN201910167560 A CN 201910167560A CN 109888233 A CN109888233 A CN 109888233A
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Abstract
The invention discloses it is a kind of can charge and discharge Grazing condition kalium ion battery, including positive electrode, negative electrode material and electrolyte；The positive electrode is KPB@CC nano material, and the negative electrode material is N, and P-VG@CC nano material, the electrolyte is KPF6, ethylene carbonate, dimethyl carbonate and fluorinated ethylene carbonate mixed solution.The invention also discloses the preparation method and applications of Grazing condition kalium ion battery.The present invention can charge and discharge Grazing condition kalium ion battery, not only increase the specific surface area and interlamellar spacing of electrode material, to effectively improve the performance of kalium ion battery, it can be applied to flexible kalium ion battery assembling, so that the reversible capacity of kalium ion battery, high rate performance and cyclical stability are improved significantly.
Description
Technical field
The present invention relates to electrochemical energy storage cell technical field, more particularly to it is a kind of can charge and discharge Grazing condition potassium ion electricity
Pond, the invention further relates to this can charge and discharge Grazing condition kalium ion battery preparation method and this can charge and discharge Grazing condition potassium ion
The application of battery.
Background technique
With the sharp increase of world population and the continuous development of human society, people increasingly increase the various demands of the energy
Long, traditional fossil energy cannot obviously meet future society to the various demands of the energy for a long time.In addition, along with fossil energy
The development and utilization in source, greenhouse effects are got worse, and ecological environment is worsening, and renewable environmentally friendly green energy resource is
As today's society question of common concern.However, wind energy, solar energy, tide energy, geothermal energy, biomass energy etc. are a series of
That often there is utilization efficiency is low for new green energy, the problem serious by regional, seasonal effect, it usually needs by it
It is converted into electric energy to be just easy to use, it is therefore desirable to which an energy storage system gets up extra energy storage, releases in demand
It releases and is utilized again.It is achieved that the deep development of new energy and efficiently utilization, the power storage that development of new is efficient, stable
Device is crucial.
Lithium ion battery due to light weight, clean and effective, have extended cycle life the advantages that big with energy density, in portable electric
Sub- equipment such as mobile phone, tablet computer etc. is commercially available widely to be applied.In recent years, with the development of new-energy automobile industry,
Lithium ion battery is gradually applied to new hybrid vehicles and pure electric automobile field, it is meant that energy market is to lithium resource
Demand sharply increase.However, rare and the unbalanced of distribution of lithium metal resource has seriously affected lithium ion battery in the earth's crust
It applies on a large scale, it is very urgent to find the new battery energy storage system that the earth's crust is resourceful, energy density is high, has extended cycle life.
The elements such as sodium, magnesium, aluminium, potassium, zinc be used to attempt to replace lithium, and among these elements, potassium and elemental lithium are in period of element
It is located at same main group in table, there are physicochemical properties similar with lithium and widely paid close attention to, especially over the past two years, potassium
Ion battery causes people and greatly pays close attention to and study.
Kalium ion battery is a kind of efficient, practical energy storage device, has resourceful, low in cost, and energy is close
Degree is high, and safe and non-toxic, advantages of environment protection makes it have broad application prospects in each application field.However, due to potassium
The radius (0.138nm) of ion is very big, therefore insertion/extraction is extremely difficult in electrochemical reaction process, this cause potassium from
The capacity of sub- battery is low, difference of magnification, service life are short.Moreover, slowing down electricity using metal collector and additive meeting blocking activity site
Son/ion transports, and reduces the energy density and flexibility of entire battery.In addition, the current overall power density of kalium ion battery,
Energy density and cycle life are still far from satisfying expected demand.Therefore, a kind of high capacity, high magnification, longevity are developed
Life can the Grazing condition kalium ion battery of charge and discharge be still current a major challenge.
Summary of the invention
For overcome the deficiencies in the prior art, one of the objects of the present invention is to provide it is a kind of can charge and discharge Grazing condition potassium from
Sub- battery, to solve, low capacity existing for above-mentioned existing kalium ion battery, difference of magnification, the service life is short, energy density is low, flexibility
The problems such as difference, overall power density, energy density and cycle life are still far from satisfying expected demand.
The second object of the present invention is to provide the preparation method of above-mentioned Grazing condition kalium ion battery, be prepared by this method
Out it is a kind of can charge and discharge Grazing condition kalium ion battery, to solve, capacity existing for above-mentioned existing kalium ion battery is low, difference of magnification, longevity
Order that short, energy density is low, flexibility is poor, overall power density, energy density and cycle life are still far from satisfying expected
The problems such as demand.
The third object of the present invention is to provide the application of above-mentioned Grazing condition kalium ion battery, to solve existing potassium ion electricity
The radius of potassium ion existing for pond is big, insertion/extraction is difficult in electrochemical reaction process, capacity is low, difference of magnification, service life are short,
Energy density is low, flexibility is poor, and overall power density, energy density and cycle life are still far from satisfying expected demand etc.
Problem.
An object of the present invention adopts the following technical scheme that realization:
It is a kind of can charge and discharge Grazing condition kalium ion battery, including positive electrode, negative electrode material and electrolyte；
The positive electrode is KPB@CC nano material, and the negative electrode material is N, P-VG@CC nano material, the electrolysis
Liquid is KPF6, ethylene carbonate, dimethyl carbonate and fluorinated ethylene carbonate mixed solution.
Further, the KPF6Concentration be 0.5~1.5M, the volume of the ethylene carbonate and dimethyl carbonate it
Than being 1~4% for the volume fraction of 1:0.5~2.5, the fluorinated ethylene carbonate.
Further, the KPF6Concentration be 0.8M, the ratio between the ethylene carbonate and the volume of dimethyl carbonate are
1:1, the volume fraction of the fluorinated ethylene carbonate are 3%.
The second object of the present invention adopts the following technical scheme that realization:
The preparation method of Grazing condition kalium ion battery described in any of the above embodiments, including preparation N, P-VG@CC nano material,
Preparation KPB@CC nano material prepares electrolyte and assembling Grazing condition kalium ion battery；
Wherein, the N, P-VG@CC nano material are prepared using following steps:
Preparation VG@CC: it is prepared in flexible carbon cloth substrate vertically using microwave plasma enhanced chemical vapour deposition technique
Graphene to get arrive VG@CC；
Prepare N, P-VG@CC nano material: adulterated using gas phase original position doping reaction into the VG@CC of preparation N, P to get
To N, P-VG@CC nano material.
Further, the preparation VG@CC includes:
It prepares flexible carbon cloth substrate: flexible carbon cloth being placed in dehydrated alcohol and is ultrasonically treated, flexibility carbon cloth substrate is made；
It prepares hydrogen plasma: flexible carbon cloth substrate being placed in quartz ampoule, is vacuumized, then is passed through H into quartz ampoule2, H2
Flow control be 100~250sccm, set the temperature of quartz ampoule as 350~500 DEG C, acquisition hydrogen plasma；
Grow VG@CC nano material: adjustment H2Flow velocity be 50~100sccm, while being passed through methane and controlling methane stream
Speed is 40~100sccm, sets growth time as 1~5h, and growth temperature is 350~500 DEG C, and VG@CC is obtained after natural cooling.
Further, during preparing hydrogen plasma, quartz ampoule is evacuated to 20mTorr, H2Flow control be
150sccm, the temperature of quartz ampoule are set as 400 DEG C；
During growing VG@CC nano material, H is adjusted2Flow velocity be 70sccm, control methane flow rate be 60sccm,
Growth time is set as 3h, growth temperature is 400 DEG C.
Further, N is prepared, P-VG@CC nano material step includes:
Preparation: VG@CC is placed in quartz ampoule and 100~500mg phosphorus is placed into quartz ampoule, is vacuumized to quartz ampoule；
N is made, P-VG@CC nano material: injects NH into quartz ampoule3, by NH3Flow control be 50~150mL
min-1, during which heated quarty tube to reaction temperature is 200~500 DEG C, and heating time is 1~3h, stops injection after natural cooling
NH3, obtain N, P-VG@CC nano material.
Further, in preliminary process, 300mg red phosphorus is placed into quartz ampoule, and be evacuated to quartz ampoule
20mTorr；
During obtained N, P-VG@CC nano material, NH3Flow control be 100mL min-1, the reaction of quartz ampoule
Temperature is 400 DEG C, heating time 2h, and heating and cooling speed are 5 DEG C of min-1。
Further, the KPB@CC nano material is prepared using following steps:
Preparation solution A: 2~10mmol FeSO is taken4·H2O and 0.2~1g PVP K-30 be dissolved in 20~100ml go from
In sub- water, stir and evenly mix to obtain solution A；
Preparation solution B: 2~10mmol K is taken4Fe(CN)6·3H2O is dissolved in 30~70ml deionized water, is stirred and evenly mixed
Obtain solution B；
Preparation KPB nano particle: solution B is added drop-wise in solution A, is stirred simultaneously during being added dropwise, quiet after 2~8h of stirring
12~50h of growth is set, KPB nano particle is made；
Prepare KPB@CC nano material: by KPB nano particle, acetylene black and Kynoar according to 60~80:15~25:
5~15 weight ratio is mixed and is dissolved in n-methyl-2-pyrrolidone, mixed slurry is made, then mixed slurry is coated
In KPB@CC nano material obtained in flexible carbon cloth substrate.
The third object of the present invention adopts the following technical scheme that realization:
The application of Grazing condition kalium ion battery described in any of the above embodiments.
In technical solution of the present invention, by regulating and controlling the pressure of plasma cvd reactor room, the stream of hydrogen
The temperature of speed and reaction chamber, to obtain hydrogen plasma；By setting flow velocity and the reaction time of hydrogen and methane, thus
Uniform VG nano-chip arrays are grown in flexible carbon cloth substrate；By setting the temperature and time in the source N and P source doping, in VG@
CC nano material Uniform Doped N atom and P atom, increase the active site and interlamellar spacing of VG@CC electrode, to keep potassium ion electric
Reversible capacity, high rate performance and the cyclical stability in pond are improved significantly.Pass through suitable concentration in setting electrolyte again
Fluorinated ethylene carbonate, so that the coulombic efficiency of Grazing condition kalium ion battery be made to be improved.On the other hand, by controlling KPB
Growth factor is coated with uniform KPB nano material in flexible carbon cloth substrate, is prepared for having flexible kalium ion battery
Positive electrode.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention can charge and discharge Grazing condition kalium ion battery, be directly prepared on flexible carbon cloth carrier KPB nanometer it is electric
Pole material and N, P-VG nano-electrode material not only increase the specific surface area and interlamellar spacing of electrode material, to effectively mention
The performance for having risen kalium ion battery can be applied to flexible kalium ion battery assembling.Meanwhile controlling fluoro carbon in electrolysis additive
The content of vinyl acetate, to improve the cyclical stability of kalium ion battery.In addition, Uniform Doped N in VG@CC nano material
Atom and P atom can further increase the active site and interlamellar spacing of VG so that the reversible capacity of kalium ion battery, times
Rate performance and cyclical stability are improved significantly.
(2) Grazing condition kalium ion battery of the present invention is capable of providing one kind in the application of electrochemical energy storage cell technical field
High capacity, high magnification, the long-life can charge and discharge Grazing condition kalium ion battery, while also having energy density high, flexible etc. excellent
Point, overall power density, energy density and cycle life can satisfy for demand expected from Grazing condition battery.
Detailed description of the invention
(a) is low range scanning electron microscope (SEM) picture of KPB in embodiment 1 in Fig. 1, is (b) height of KPB in embodiment 1
Multiplying power scanning electron microscope (SEM) picture；
(a) is X-ray powder diffraction (XRD) picture of KPB in embodiment 1 in Fig. 2, is (b) XPS of KPB in embodiment 1
Full spectrogram piece is (c) the P 2p high-resolution XPS picture of KPB in embodiment 1；
(a) is high magnification scanning electron microscope (SEM) picture of VG@CC in embodiment 1 in Fig. 3, is (b) N, P- in embodiment 1
High magnification scanning electron microscope (SEM) picture of VG@CC；
(a) is N in embodiment 1 in Fig. 4, and transmission electron microscope (TEM) picture of P-VG@CC is (b) VG@CC in embodiment 1
Transmission electron microscope (TEM) picture is (c) VG, VG@CC and N in embodiment 1, X-ray powder diffraction (XRD) picture of P-VG@CC；
Fig. 5 is N in embodiment 1, and the X-ray energy spectrum of P-VG@CC analyzes (EDS) picture；
(a) is VG@CC and N in embodiment 1 in Fig. 6, the full spectrogram piece of the x-ray photoelectron spectroscopy (XPS) of P-VG@CC,
(b), (c), (d) are respectively C 1s in embodiment 1, and the high-resolution XPS picture of N 1s and P 2p are (e) N, P- in embodiment 1
The atom percentage content of the N and P of VG@CC；
Fig. 7 is the constant current charge-discharge curve of Grazing condition kalium ion battery in embodiment 1；
Fig. 8 is the high rate performance of Grazing condition kalium ion battery in embodiment 1；
Fig. 9 is the cycle performance of Grazing condition kalium ion battery in embodiment 1；
Figure 10 is constant-current discharge curve of the Grazing condition kalium ion battery under differently curved state in embodiment 1.
Specific embodiment
In the following, being described further in conjunction with attached drawing and specific embodiment to the present invention, it should be noted that not
Under the premise of conflicting, new implementation can be formed between various embodiments described below or between each technical characteristic in any combination
Example.
Embodiment 1
Can charge and discharge Grazing condition kalium ion battery, including positive electrode, negative electrode material and electrolyte.Wherein, positive electrode
For KPB@CC nano material, negative electrode material N, P-VG@CC nano material, electrolyte KPF6, ethylene carbonate, carbonic acid diformazan
The mixed solution of ester and fluorinated ethylene carbonate.
The preparation process of KPB@CC nano material is as follows:
Preparation solution A: 4mmol FeSO is taken4·H2O and 0.4g PVP K-30 (i.e. polyvinylpyrrolidone) is dissolved in
It in 40ml deionized water, is mixed by magnetic stirrer, obtains solution A.
Preparation solution B: 4mmol K is taken4Fe(CN)6·3H2O is dissolved in 50ml deionized water, is stirred by magnetic stirring apparatus
Mixing is mixed, solution B is obtained.
Preparation KPB nano particle: solution B is added drop-wise in solution A, is stirred continuously during being added dropwise, and the total 3h of duration is stirred
Afterwards, mixed solution is stood into growth 48h, KPB nano particle is made.
Prepare KPB@CC nano material: the weight by KPB nano particle, acetylene black and Kynoar according to 70:20:10
Ratio mixing, is dissolved in the n-methyl-2-pyrrolidone of 3ml after mixing and mixed slurry is made.In advance by commercial carbon cloth (size
It is placed in dehydrated alcohol for 2 × 3cm) after being ultrasonically treated 15min and serves as flexible substrates.It is again that the mixed slurry of above-mentioned preparation is manual
It is evenly applied in flexible carbon cloth substrate, above-mentioned flexible carbon cloth substrate is put into oven drying 12 hours of 70 DEG C, carrying capacity is obtained
For 2mgcm-2KPB@CC positive electrode.
The preparation process of N, P-VG@CC nano material is as follows:
Flexibility is served as step 1: commercial carbon cloth (size is 2 × 3cm) is placed in dehydrated alcohol after ultrasonic treatment 15min
Carbon cloth substrate.Commercial carbon cloth is placed in ultrasonic treatment in dehydrated alcohol can remove the grease of commercial carbon cloth surfaces, side well
Phase vertical graphene (Vertical graphene, VG) is in the growth course of commercial carbon cloth after an action of the bowels.
Step 2: commercial carbon cloth to be placed in the center of the quartz ampoule of microwave plasma, then quartz ampoule is vacuumized
To 20mTorr.
Step 3: being passed through H into the above-mentioned quartz ampoule vacuumized2, by H2Flow control be 150sccm, microwave plasma
The power control of body is 750W, when the temperature of system is increased to 400 DEG C, obtains hydrogen plasma.
Step 4: adjusting the flow velocity of hydrogen in the above-mentioned quartz ampoule vacuumized in the growth course of vertical graphene
Methane is injected simultaneously, the flow velocity of hydrogen and methane is respectively set to 70sccm and 60sccm, the growth course duration is
3h, being during which continually fed into hydrogen and methane to growth course terminates.VG@CC is obtained after natural cooling.
Step 5: the VG@CC that the 4th step obtains to be placed in the center of the quartz ampoule of microwave plasma, side places one
A porcelain boat for holding 300mg red phosphorus.
Step 6: injecting NH after the quartz ampoule in above-mentioned 5th step is evacuated to 20mTorr3, by NH3Flow control
For 100mL min-1, it is continually fed into NH3。
Step 7: 400 DEG C, heating time 120min, VG@CC completion N, P doping processes are set by the reaction temperature,
Obtain the VG@CC nano material of N, P doping.
Step 8: being continually fed into NH3, after the VG@CC nano material natural cooling of to be prepared N, P doping, obtain N, P-
VG@CC nano material, stopping are passed through NH3。
The preparation process of electrolyte is as follows:
Each 1ml of ethylene carbonate, dimethyl carbonate is taken, ethylene carbonate and dimethyl carbonate volume are made after mixing
Than the mixed solution for 1:1.KPF is added into mixed solution6To KPF6Concentration be 0.8M, while being added into mixed solution
Fluorinated ethylene carbonate to its volume fraction is 5%, thus prepares electrolyte.
The assembling process of Grazing condition kalium ion battery is as follows:
The assembling of flexible kalium ion battery is completed in vacuum glove box, and the water oxygen content of vacuum glove box is
0.1ppm.By the N of preparation, P-VG@CC is directly as negative electrode material, and KPB@CC nano material is as positive electrode.Positive electrode
It is tailored to the rectangle of 2cm × 3cm before assembling with negative electrode material, (businessman: Britain's water is graceful, grade for glass microfiber film
It is other: GF/B) it is used as diaphragm.Positive electrode, diaphragm and negative electrode material are loaded with aluminium package, electrolyte then is added dropwise toward aluminium packet
Until soaking positive electrode, diaphragm and negative electrode material all.It is finally encapsulated with sealing machine and has just obtained Grazing condition potassium
Ion battery.
Effect example 1
The test of Flied emission scanning electron microscopy Electronic Speculum is carried out to the above-mentioned KPB nano material being prepared, as a result such as Fig. 1
It is shown, show that KPB nano material is cubic shaped.
X-ray powder diffraction (XRD) and x-ray photoelectron spectroscopy have been carried out to the above-mentioned KPB nano material being prepared
(XPS) other impurity peaks, table is not observed as a result as shown in Fig. 2, other than the characteristic peak of KPB nano material in characterization
The bright KPB nano material for being successfully prepared high-purity.
To VG the@CC and N of above-mentioned preparation, P-VG@CC electrode has carried out the test of Flied emission scanning electron microscopy Electronic Speculum, as a result
As shown in figure 3, grown uniform vertical graphene nano chip arrays (Fig. 3 a) on flexible carbon cloth fiber, and N and P atom
After doping in situ, show that surface topography does not change significantly (Fig. 3 b).
To VG the@CC and N of above-mentioned preparation, P-VG@CC carries out high resolution TEM (HRTEM) and x-ray powder spreads out
(XRD) characterization is penetrated, Fig. 4 a shows N, and the interlamellar spacing of P-VG@CC is 0.36nm, and the interlamellar spacing of Fig. 4 b display VG@CC is
0.34nm shows vertical graphene by N, and the interlamellar spacing after P doping becomes larger.
To the N of above-mentioned preparation, P-VG@CC carries out X-ray energy spectrum analysis (EDS) characterization, as a result as shown in figure 5, show N and
P atom has successfully been doped to the surface of vertical graphene.
X-ray photoelectron spectroscopy (XPS) characterization is carried out to the N of above-mentioned preparation, P-VG@CC, as a result as shown in fig. 6, showing N
The surface of vertical graphene is successfully doped to P atom, and the atomic percentage content of N and P is respectively 3.85% He
7.53%.
Effect example 2
Grazing condition potassium ion electricity is studied using constant current charge-discharge test method to the Grazing condition kalium ion battery of above-mentioned preparation
The energy-storage property in pond, the constant current charge-discharge test of Grazing condition potassium ion are at room temperature, newly to complete on Weir battery test system
, the voltage window of test is 2.0-4.0V.
As shown in Figure 7, by discharge curve as can be seen that this Grazing condition kalium ion battery has the voltage close to 4.0V,
And there are longer discharge platform, high reversible.
As shown in Figure 8, the range of capacity of the Grazing condition kalium ion battery of above-mentioned preparation is from 50mA g-1When 116.25mA h
g-1Change to 2000mA g-150.67mA h g-1, and pass through 30 profound charge and discharge, when current density is restored to
50mA g-1When, reversible capacity can still remain 102.13mA h g-1, show it with good high rate performance.
As shown in Figure 9, the Grazing condition kalium ion battery is in 50mA g-1Current density under after continuous charge and discharge 150 times still
There is 86.9% capacity retention ratio, shows that the Grazing condition kalium ion battery has good cyclical stability.This figure is that double Y-axis are total
X-axis figure, the wherein corresponding capacity of left y axis, and it is coulombic efficiency that right Y axis is corresponding.The left arrow of three lines below in the figure
Head be directed toward left y axis the capacity corresponding to Grazing condition kalium ion battery, above three lines with right arrow direction right Y axis pair
Should be in the coulombic efficiency of Grazing condition kalium ion battery, coulombic efficiency is higher, shows that cyclical stability is better.
Flexible test has been carried out to the Grazing condition kalium ion battery, as shown in Figure 10, no matter the Grazing condition potassium ion
Battery is under unbending state, or in the state of 90-degree bent, or be in the state of being bent 135 °, capacity and
Discharge curve there is no apparent variation occurs, illustrate the Grazing condition kalium ion battery can under any bending state use without
Discharge curve and capacity can be damaged.Therefore, which arbitrarily can be bent or distort discharges without damaging
Curve and capacity.
In conclusion this Grazing condition kalium ion battery has large capacity, high magnification, the long-life repeats charge and discharge,
It has great application prospect in terms of energy storage.
Embodiment 2-4
The preparation method of embodiment 2-4 is same as Example 1, and difference is VG hydrogen when growing in flexible carbon cloth substrate
The flow velocity of gas and methane.Specific flow velocity regulation is shown in Table 1 in the preparation method of embodiment 2-4.The N prepared using embodiment 2-4,
P-VG@CC nano material carries out assembling and prepares Grazing condition kalium ion battery, referring to the identical constant current charge and discharge of said effect embodiment 2
Electrical testing method studies the energy-storage property of Grazing condition kalium ion battery.Grazing condition kalium ion battery prepared by embodiment 1 is in 50mA
g-1When corresponding specific capacity be 116.25mA h g-1, the Grazing condition kalium ion battery of testing example 2-4 preparation is in 50mA g-1
When corresponding specific capacity.
The regulation of the flow velocity of 1 hydrogen of table and methane
Embodiment 5-7
The preparation method of embodiment 5-7 is same as Example 1, difference be VG when being grown in flexible carbon cloth substrate,
Temperature, the time for adulterating heating are different.Heating time, the heating of heating are specifically adulterated in the preparation method of embodiment 5-7
Temperature is shown in Table 2.The N prepared using embodiment 5-7, P-VG@CC nano material are carried out assembling and prepare Grazing condition kalium ion battery, are joined
The energy-storage property of Grazing condition kalium ion battery is studied according to the identical constant current charge-discharge test method of said effect embodiment 2.Implement
Still there are 86.9% capacity retention ratio, testing example 5- after prepared by example 1 the continuous charge and discharge of Grazing condition kalium ion battery 150 times
Capacity retention ratio after the continuous charge and discharge of Grazing condition kalium ion battery 150 times of 7 preparations.
The heating time of the doping heating of table 2, heating temperature regulation
Embodiment 8-10
The preparation method of embodiment 8-10 is same as Example 1, and difference is that KPB growth time regulates and controls.Embodiment 8-
Specific growth time is shown in Table 3 in 10 preparation method.It is complete that assembling preparation is carried out using KPB nano material prepared by embodiment 8-10
Flexible kalium ion battery studies Grazing condition potassium ion electricity referring to the identical constant current charge-discharge test method of said effect embodiment 2
The energy-storage property in pond.Grazing condition kalium ion battery prepared by embodiment 1 is in 50mA g-1When corresponding specific capacity be 116.25mA h
g-1, the Grazing condition kalium ion battery of testing example 8-10 preparation is in 50mA g-1When corresponding specific capacity.
The growth time of 3 KPB of table regulates and controls
Embodiment 11-13
The preparation method of embodiment 11-13 is same as Example 1, and difference is fluorinated ethylene carbonate in electrolyte
Content.Specific fluorinated ethylene carbonate content is shown in Table 4 in the preparation method of embodiment 11-13.It is prepared using embodiment 11-13
Fluorinated ethylene carbonate electrolyte carry out assembling and prepare Grazing condition kalium ion battery, it is identical referring to said effect embodiment 2
Constant current charge-discharge test method studies the energy-storage property of Grazing condition kalium ion battery.Grazing condition potassium ion electricity prepared by embodiment 1
Still there are 86.9% capacity retention ratio, the Grazing condition potassium ion electricity of testing example 11-13 preparation after the continuous charge and discharge in pond 150 times
Capacity retention ratio after the continuous charge and discharge in pond 150 times.
The content of 4 fluorinated ethylene carbonate of table regulates and controls
The above embodiment is only the preferred embodiment of the present invention, and the scope of protection of the present invention is not limited thereto,
The variation and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to institute of the present invention
Claimed range.
Claims (10)
1. one kind can charge and discharge Grazing condition kalium ion battery, which is characterized in that including positive electrode, negative electrode material and electrolyte；
The positive electrode is KPB@CC nano material, and the negative electrode material is N, and P-VG@CC nano material, the electrolyte is
KPF6, ethylene carbonate, dimethyl carbonate and fluorinated ethylene carbonate mixed solution.
2. Grazing condition kalium ion battery according to claim 1, which is characterized in that the KPF6Concentration be 0.5~
The ratio between volume of 1.5M, the ethylene carbonate and dimethyl carbonate is 1:0.5~2.5, the body of the fluorinated ethylene carbonate
Fraction is 1~4%.
3. Grazing condition kalium ion battery according to claim 2, which is characterized in that the KPF6Concentration be 0.8M, it is described
The ratio between volume of ethylene carbonate and dimethyl carbonate is 1:1, the volume fraction 3% of the fluorinated ethylene carbonate.
4. the preparation method of Grazing condition kalium ion battery according to claim 1-3, which is characterized in that including system
Standby N, P-VG@CC nano material, prepare electrolyte and assembling Grazing condition kalium ion battery at preparation KPB@CC nano material；
Wherein, the N, P-VG@CC nano material are prepared using following steps:
Preparation VG@CC: vertical graphite is prepared in flexible carbon cloth substrate using microwave plasma enhanced chemical vapour deposition technique
Alkene to get arrive VG@CC；
Prepare N, P-VG@CC nano material: adulterate using gas phase original position doping reaction into the VG@CC of preparation N, P to get arrive N,
P-VG@CC nano material.
5. the preparation method of Grazing condition kalium ion battery according to claim 4, which is characterized in that the preparation VG@CC
Include:
It prepares flexible carbon cloth substrate: flexible carbon cloth being placed in dehydrated alcohol and is ultrasonically treated, flexibility carbon cloth substrate is made；
It prepares hydrogen plasma: flexible carbon cloth substrate being placed in quartz ampoule, is vacuumized, then is passed through H into quartz ampoule2, H2Stream
Speed control is 100~250sccm, sets the temperature of quartz ampoule as 350~500 DEG C, obtains hydrogen plasma；
Grow VG@CC nano material: adjustment H2Flow velocity be 50~100sccm, while be passed through methane and control methane flow rate be 40
~100sccm sets growth time as 1~5h, and growth temperature is 350~500 DEG C, and VG@CC is obtained after natural cooling.
6. the preparation method of Grazing condition kalium ion battery according to claim 5, which is characterized in that
During preparing hydrogen plasma, quartz ampoule is evacuated to 20mTorr, H2Flow control be 150sccm, quartz ampoule
Temperature be set as 400 DEG C；
During growing VG@CC nano material, H is adjusted2Flow velocity be 70sccm, control methane flow rate be 60sccm, setting give birth to
It is for a long time 3h, growth temperature is 400 DEG C.
7. the preparation method of Grazing condition kalium ion battery according to claim 4, which is characterized in that preparation N, P-VG@CC
Nano material step includes:
Preparation: VG@CC is placed in quartz ampoule and 100~500mg phosphorus is placed into quartz ampoule, is vacuumized to quartz ampoule；
N is made, P-VG@CC nano material: injects NH into quartz ampoule3, by NH3Flow control be 50~150mL min-1, the phase
Between heated quarty tube to reaction temperature be 200~500 DEG C, heating time is 1~3h, stops injection NH after natural cooling3, obtain
N, P-VG@CC nano material.
8. the preparation method of Grazing condition kalium ion battery according to claim 7, which is characterized in that
In preliminary process, 300mg red phosphorus is placed into quartz ampoule, and 20mTorr is evacuated to quartz ampoule；
During obtained N, P-VG@CC nano material, NH3Flow control be 100mL min-1, the reaction temperature of quartz ampoule
It is 400 DEG C, heating time 2h, heating and cooling speed are 5 DEG C of min-1。
9. the preparation method of Grazing condition kalium ion battery according to claim 4, which is characterized in that CC nanometers of the KPB@
Material is prepared using following steps:
Preparation solution A: 2~10mmol FeSO is taken4·H2O and 0.2~1g PVP K-30 are dissolved in 20~100ml deionized water
In, it stirs and evenly mixs to obtain solution A；
Preparation solution B: 2~10mmol K is taken4Fe(CN)6·3H2O is dissolved in 30~70ml deionized water, stirs and evenly mixs to obtain
Solution B；
Preparation KPB nano particle: solution B is added drop-wise in solution A, is stirred simultaneously during being added dropwise, and stands life after stirring 2~8h
Long 12~50h, is made KPB nano particle；
Prepare KPB@CC nano material: by KPB nano particle, acetylene black and Kynoar according to 60~80:15~25:5~
15 weight ratio is mixed and is dissolved in n-methyl-2-pyrrolidone, mixed slurry is made, then by mixed slurry coated on soft
Property carbon cloth substrate on be made KPB@CC nano material.
10. the application of the described in any item Grazing condition kalium ion batteries of claim 1-3.
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