CN109285991A - A kind of preparation method and application of flexible compound electrode - Google Patents
A kind of preparation method and application of flexible compound electrode Download PDFInfo
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- CN109285991A CN109285991A CN201811207507.9A CN201811207507A CN109285991A CN 109285991 A CN109285991 A CN 109285991A CN 201811207507 A CN201811207507 A CN 201811207507A CN 109285991 A CN109285991 A CN 109285991A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- 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
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation method and applications of flexible compound electrode.The preparation method of this flexible compound electrode adds carbon nanotube, is uniformly dispersed, obtain dispersion liquid the following steps are included: 1) cellulosic material is dissolved in solvent；2) it by the positive electrode of metal ion battery or negative electrode material investment dispersion liquid, is uniformly dispersed, filters film forming；3) membrane material is washed, dry, compression moulding obtains flexible compound electrode.The application of this flexible compound electrode is also disclosed simultaneously.The present invention passes through simple preparation process, a kind of alkali metal-ion battery composite and flexible electrode without metal collector and other conductive agents, binder is obtained, the combination electrode chemical property is also more excellent simultaneously, and can also be suitable for doing positive/negative flexible current-collecting body simultaneously.
Description
Technical field
The present invention relates to a kind of preparation method and applications of flexible compound electrode.
Background technique
Today's society new energy is eternal development topic, from fossil energy solar energy till now, wind energy, tide energy,
Geothermal energy etc., the paces that the mankind explore never stop.Lithium ion battery as a member in new energy family, it with its environmental protection,
The advantages such as convenient, safety, low cost, excellent electrical property and by it is believed that being one of fossil energy best substitute.It is same with this
When, sodium-ion battery is cheap because its is from a wealth of sources, requires electrolyte low, and without over-discharge electrical phenomena the advantages that is also ground
The persons of studying carefully are good.Multiphase crystal class ferric flouride makees positive electrode, and voltage platform can reach 2.74V, work as 3e-When shifting completely, reason
712mAh/g, 1e can be reached by specific capacity-When transfer, theoretical specific capacity can reach 237mAh/g, its derivative has six side's blue copper
Type FeF3·0.33H2O, pyrochlore-type FeF3·0.5H2O, pyrochlore-type FeF2.5·0.5H2O, unformed FeOF etc..Solely because of it
Special crystal structure and be provided with and compare Li+(radius is) and Na+(radius is) the bigger micropore of radius, to make
It obtains the material and is provided simultaneously with Li+/Na+It is embedded in the ability of abjection；Prussian-blue has typical cubic structure,
There is biggish gap between its space lattice, also can well be Li+/Na+Reversible deintercalation site and diffusion admittance are provided.
In order to preferably meet pursuit of the people to good life, wearable portable flexible battery is seasonable and gives birth to.It is flexible
Battery will meet do not damage electronics on the basis of can be carried out it is any bending, fold and stretching, extension, this just proposes the production of battery material
New challenge is gone out.The key of flexible battery is flexible electrode, and electrode is needed not occur electricity while meeting flexible demand
Phenomena such as pole piece picking, fracture.Currently, common flexible current-collecting body is mainly using carbon cloth, carbonized fabric etc. as flexible current-collecting
Body, often electric conductivity is bad for the flexible current-collecting body that this method obtains, and pole piece is thicker；In addition, also having using graphene, carbon
The flexible electrode of nanotube and polymer composition metal nano wire, although performance is more excellent, higher cost, ductility are not
It is enough.Therefore, it is crucial for finding the flexible current-collecting body that a kind of electric conductivity is excellent, thickness is smaller, cost is relatively low and ductility is good.
Prior art discloses the reports of some associated batteries electrode materials: a kind of potassium/sodium-ion battery is with opening frame fluorine
It is to do product although using ferric flouride analog derivative in compound positive electrode and preparation method thereof (CN107104248A)
Raw material, and be unused for directly as flexible sodium-ion battery positive material.One kind being based on carbon nanotube-graphene compound three
Tie up the FeF of network3The preparation method of flexible motor and application (CN104183832A) are multiple using graphene and carbon nanotube simultaneously
It closes borontrifluoride iron and does flexible electrode, it is not only at high cost, and it is not applied to sodium-ion battery.A kind of lithium ion battery branch certainly
The self-supporting flexible carbon nano-tube paper in flexible carbon nano-tube paper composite electrode material (CN102593436A) is supportted, needs pipe range non-
Often long carbon nanotube (price can be somewhat expensive) could form paper, and due to not adding any structural support agent, gained flexibility carbon
Nanotube paper intensity can be lower, and flexible effect will not be highly desirable.The preparation method of electrode material and electrode material prepared therefrom
(CN105206431A) although in also prepare electrode using materials such as nano cellulose crystal and carbon nanotubes, it is not mentioned
And its material is used to prepare lithium/sodium-ion battery flexible electrode material, and the preparation method and flexible electrical of its silica aerogel electrode
Pole preparation method is also different.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method and applications of flexible compound electrode, are related to new energy battery side
To for providing the lithium, sodium or kalium ion battery flexible electrode material of daily life.
The technical solution used in the present invention is:
A kind of preparation method of flexible compound electrode, comprising the following steps:
1) cellulosic material is dissolved in solvent, adds carbon nanotube, be uniformly dispersed, obtain dispersion liquid；
2) it by the positive electrode of metal ion battery or negative electrode material investment dispersion liquid, is uniformly dispersed, filters film forming；
3) membrane material is washed, dry, compression moulding obtains flexible compound electrode.
In the step 1) of preparation method, the mass ratio of carbon nanotube and cellulosic material is (1~9): 1.
In the step 1) of preparation method, cellulosic material is microcrystalline cellulose, Cellulose nanocrystal palpus, Nano bacteria
It is at least one of plain, cellulose nano-fibrous.
In the step 1) of preparation method, the pipe range of carbon nanotube is 10 μm~100 μm.
In the step 1) of preparation method, solvent is water, ethyl alcohol, acetone, ether, N-Methyl pyrrolidone, N, N- dimethyl
At least one of formamide, tetrahydrofuran, dimethyl sulfoxide, ionic liquid.
Preparation method step 1) is separated into ultrasonic disperse, and the time of ultrasonic disperse is 0.5h~4h.
In the step 2) of preparation method, the positive electrode of metal ion battery is iron-based fluoride, Prussian blue similar object
At least one of.
In the step 2) of preparation method, the negative electrode material of metal ion battery is hard carbon, graphene, graphite, silicon-carbon, silicon substrate
Oxide, Li4Ti5O12、Na3V2(PO4)3、Na2Ti6O13At least one of.
Preparation method step 2) is separated into ultrasonic disperse, and the time of ultrasonic disperse is 1min~10min.
In the step 3) of preparation method, compression moulding is to be compacted in twin rollers with the pressure of 10MPa~120MPa.
A kind of flexible electrode of alkali metal-ion battery is flexible compound electrode made from aforementioned preparation process.
The beneficial effects of the present invention are:
The present invention has obtained one kind without metal collector and other conductive agents, binder by simple preparation process
Alkali metal-ion battery composite and flexible electrode, while the combination electrode chemical property is also more excellent, and can also be simultaneously
Suitable for doing positive/negative flexible current-collecting body.
Compared with prior art, advantages of the present invention is as follows:
1) a kind of perfect alkali metal-ion battery composite and flexible electrode preparation method, and preparation process can be directly provided
Simply；
2) combination electrode cost of the invention is lower, and electric conductivity is excellent, thickness is smaller, without additional binder, and
Ductility is good；
3) active material in combination electrode of the present invention can be preferably distributed in inside collector, compared in other metals
Active material is directly coated on collector and flexible current-collecting body, it has thinner thickness of electrode, thus flexible same in guarantee
Shi Yineng effectively promotes the energy density of battery；
4) activated species that the preparation method of combination electrode of the present invention can be attached to by simple replacement, to meet
Make the needs of different lithium/sodium ions to potassium ions battery flexible electrode；
5) present invention obtains combination electrode after low pressure is to roller, and other than thickness is thinning, flexible and intensity can be had
Effect is promoted.
Detailed description of the invention
Fig. 1 is the flow diagram of flexible compound electrode preparation；
Fig. 2 is the XRD diagram of positive electrode obtained by Examples 1 and 2；
Fig. 3 is the scanning electron microscope (SEM) photograph of 1 gained positive electrode of embodiment；
Fig. 4 is the section electron microscope of 1 gained anode composite film of embodiment；
Fig. 5 is the scanning electron microscope (SEM) photograph of 2 gained positive electrode of embodiment；
Fig. 6 is the pictorial diagram that comparative example 1 obtains；
Fig. 7 is the pictorial diagram that comparative example 2 obtains；
Fig. 8 is the scanning electron microscope (SEM) photograph of comparative example 2；
Fig. 9 is first charge-discharge curve graph of the 1 flexible compound electrode assembling of embodiment at lithium ion battery；
Figure 10 is first charge-discharge curve graph of the 1 flexible compound electrode assembling of embodiment at sodium-ion battery；
Figure 11 is first charge-discharge curve graph of the 2 flexible compound electrode assembling of embodiment at lithium ion battery；
Figure 12 is first charge-discharge curve graph of the 2 flexible compound electrode assembling of embodiment at sodium-ion battery.
Specific embodiment
A kind of preparation method of flexible compound electrode, comprising the following steps:
1) cellulosic material is dissolved in solvent, adds carbon nanotube, be uniformly dispersed, obtain dispersion liquid；
2) it by the positive electrode of metal ion battery or negative electrode material investment dispersion liquid, is uniformly dispersed, filters film forming；
3) membrane material is washed, dry, compression moulding obtains flexible compound electrode.
Preferably, in the step 1) of preparation method, the mass ratio of carbon nanotube and cellulosic material is (1~9): 1.
Preferably, in the step 1) of preparation method, cellulosic material is microcrystalline cellulose, Cellulose nanocrystal palpus, bacterium
At least one of nano-cellulose, cellulose nano-fibrous.
Preferably, in the step 1) of preparation method, the pipe range of carbon nanotube is 10 μm~100 μm.
Preferably, in the step 1) of preparation method, carbon nanotube be multi-walled carbon nanotube, in single-walled carbon nanotube at least
It is a kind of.
Preferably, in the step 1) of preparation method, solvent is water, ethyl alcohol, acetone, ether, N-Methyl pyrrolidone, N, N-
At least one of dimethylformamide, tetrahydrofuran, dimethyl sulfoxide, ionic liquid；It is further preferred that solvent be water,
At least one of ethyl alcohol, acetone, N-Methyl pyrrolidone, ionic liquid.
Preferably, preparation method step 1) is separated into ultrasonic disperse, and the time of ultrasonic disperse is 0.5h~4h.
Preferably, in the step 2) of preparation method, the solid masses of metal ion cell positive material or negative electrode material with
The volume ratio of dispersion liquid is 1g:(5~50) mL.
Preferably, in the step 2) of preparation method, metal ion battery is alkali metal-ion battery；It is further preferred that
Metal ion battery is flexible alkali metal-ion battery；Still further preferably, metal ion battery be flexible lithium ion battery,
At least one of flexible sodium-ion battery, flexible kalium ion battery.
Preferably, in the step 2) of preparation method, the positive electrode of metal ion battery is flexible alkali metal-ion battery
Positive electrode, at least one of specially iron-based fluoride, Prussian blue similar object；Wherein, iron-based fluoride is
FeF3·0.33H2O、FeF3·0.5H2O、FeF2.5·0.5H2O, at least one of FeOF；Prussian blue similar object is Fe-
At least one of HCF, Co-HCF, Ni-HCF, Mn-HCF, Cu-HCF, Zn-HCF.
Preferably, in the step 2) of preparation method, the negative electrode material of metal ion battery is hard carbon, graphene, graphite, silicon
Carbon, silicon-base oxide, Li4Ti5O12、Na3V2(PO4)3、Na2Ti6O13At least one of.
Further, in the step 2) of preparation method, the positive electrode or negative electrode material of metal ion battery are by normal
What the synthetic method seen obtained, so-called common synthetic method is high temperature solid-state method, solvent-thermal method, ionic liquid, co-precipitation
One of method, sol-gal process, spray drying process, vapour deposition process are a variety of.
Preferably, in the step 2) of preparation method, in dispersion liquid mass percent shared by active material be 50%~
90%.
Preferably, preparation method step 2) is separated into ultrasonic disperse, and the time of ultrasonic disperse is 1min~10min.
Preferably, in the step 2) of preparation method, film forming is filtered for vacuum filtration film forming, specially in 0.45 μm of micropore
Vacuum filtration film forming is carried out on filter membrane.
Preferably, in the step 3) of preparation method, compression moulding be in twin rollers with the pressure of 10MPa~120MPa into
Row compacting；It is further preferred that the pressing pressure of twin rollers is 10MPa~60MPa.
A kind of flexible electrode of alkali metal-ion battery is flexible compound electrode made from aforementioned preparation process.
Preferably, the flexible electrode of this alkali metal-ion battery is lithium ion battery and/or sodium-ion battery and/or potassium
The flexible electrode of ion battery.
The invention discloses it is a kind of and meanwhile it is conductive can it is excellent, thickness is smaller, cost is relatively low and ductility is preferable
The preparation method of novel flexible alkali metal-ion battery electrode.The method of the present invention mainly passes through preparation one kind can allow alkali metal simultaneously
The microporous crystal positive electrode of ion intercalation/deintercalation；Carbon nanotube is added in such positive electrode again and cellulosic material disperses
Disperse in liquid, form a film through vacuum filtration, wash drying, low pressure obtains flexible compound electrode to roller.
The contents of the present invention are described in further detail below by way of specific embodiment.Original used in embodiment
Material unless otherwise specified, can be obtained from routine business approach.
Embodiment 1
FeF is synthesized using ionic liquid3·0.5H2O, the specific steps are that:
By 2g Fe (NO3)3·9H2O and excessive 1- butyl -3- methyl imidazolium tetrafluoroborate (BmimBF4) are in 10mL
With 120 DEG C of solvent thermal reaction 8h in dehydrated alcohol, washed drying directly obtains yellow FeF3·0.5H2O positive pole powder.Gained is just
Pole material XRD diagram is as shown in Fig. 2, and SEM figure is as shown in Fig. 3.
The preparation step of 1 flexible composite electrode material of embodiment is as follows:
First take 0.05g Cellulose nanocrystal must in 20mL deionized water strength ultrasonic disperse at clear gum, then will pipe
A length of 20 μm of carbon nanotube and Cellulose nanocrystal must the ratio of 4:1 in mass ratio be added thereto, and continue ultrasonic disperse 3h,
The above-mentioned FeF of 0.5g is added thereto again3·0.5H2O positive pole powder (active material accounting 67%) continues ultrasound 2min, by gained
Mixture dispersion liquid directly carries out vacuum filtration film forming on 0.45 μm of miillpore filter, washs drying, and combination electrode film of tearing is put
Enter and be compacted in the twin rollers under 20MPa pressure, obtains the flexible compound electrode of embodiment 1, section SEM such as 4 institute of attached drawing
Show, section thickness is 122.8 μm.
Embodiment 2
FeF is synthesized using liquid phase method3·0.33H2O, the specific steps are that:
By 2g Fe (NO3)3·9H2O and excessive NH4F2It stirs and stands in the mixed liquor of 15mL dehydrated alcohol and 5mL water
12h obtains bulky grain presoma, is put into 240 DEG C of tube furnaces of Ar atmosphere after washed drying and is sintered 3h, obtains yellow FeF3·
0.33H2O positive pole powder.Gained positive electrode XRD diagram is as shown in Fig. 2, and SEM figure is as shown in Fig. 5.
The preparation step of 2 flexible composite electrode material of embodiment is as follows:
First take 0.05g Nano bacteria cellulose in 30mL deionized water strength ultrasonic disperse at clear gum, then will pipe
A length of 80 μm of carbon nanotube and the Nano bacteria cellulose ratio of 5:1 in mass ratio are added thereto, and continue ultrasonic disperse
2.5h, then the above-mentioned FeF of 0.5g is added thereto3·0.33H2O positive pole powder (active material accounting 63%) continues ultrasound 1min,
Gained mixture dispersion liquid is directly subjected to vacuum filtration film forming on 0.45 μm of miillpore filter, washs drying, compound electric of tearing
Pole film is compacted in the twin rollers being put under 30MPa pressure, obtains the flexible compound electrode of embodiment 2.
Embodiment 3
FeF is synthesized using ionic liquid2.5·0.5H2O, the specific steps are that:
By 2g Fe (NO3)3·9H2O and excessive ionic liquid BmimBF4 is in 10mL dehydrated alcohol with 80 DEG C of solvent heats
React 10h, washed drying directly light yellow FeF3·0.5H2O positive pole powder.
The preparation step of 3 flexible composite electrode material of embodiment is as follows:
First take the cellulose nano-fibrous strength ultrasonic disperse in 40mL deionized water of 0.05g at clear gum, then will pipe
A length of 100 μm of carbon nanotube and the cellulose nano-fibrous ratio of 7:1 in mass ratio are added thereto, and continue ultrasonic disperse
2h, then the above-mentioned FeF of 0.5g is added thereto2.5·0.5H2O positive pole powder (active material accounting 56%) continues ultrasound 3min,
Gained mixture dispersion liquid is directly subjected to vacuum filtration film forming on 0.45 μm of miillpore filter, washs drying, compound electric of tearing
Pole film is compacted in the twin rollers being put under 40MPa pressure, obtains the flexible compound electrode of embodiment 3.
Embodiment 4
Using solvent structure FeOF, the specific steps are that:
The 2g FeF that high temperature solid-state method is synthesized3·3H2O disperses in 10mL normal propyl alcohol, places into polytetrafluoroethylene (PTFE) bottle
220 DEG C are carried out, 20h solvent thermal reaction obtains FeOF positive pole powder after washed drying.
The preparation step of 4 flexible composite electrode material of embodiment is as follows:
0.05g microcrystalline cellulose strength ultrasonic disperse in 40mL deionized water is first taken at clear gum, then by pipe range to be
100 μm of carbon nanotube and the microcrystalline cellulose ratio of 6:1 in mass ratio is added thereto, and continues ultrasonic disperse 4h, then to its
The middle above-mentioned FeOF positive pole powder of addition 0.6g (active material accounting 63%) continues ultrasound 4min, by gained mixture dispersion liquid
Vacuum filtration film forming is directly carried out on 0.45 μm of miillpore filter, washs drying, and combination electrode film of tearing is put into 30MPa pressure
Under twin rollers in be compacted, obtain the flexible compound electrode of embodiment 4.
Embodiment 5
Prussian blue similar object is synthesized using liquid phase method, the specific steps are that:
By 2g Na4Fe(CN)6·10H2O is dissolved in deionized water, and is instilled 1.67gFeSO4·7H2O and 15g lemon
In sour sodium mixed solution, after mixing, room temperature keeps 6h, and washed, dry 12h, obtains iron-based in 80 DEG C of vacuum ovens
Prussian blue similar object positive pole powder.
The preparation step of 5 flexible composite electrode material of embodiment is as follows:
First take the cellulose nano-fibrous strength ultrasonic disperse in 20mL deionized water of 0.05g at clear gum, then will pipe
A length of 50 μm of carbon nanotube and the cellulose nano-fibrous ratio of 3:1 in mass ratio are added thereto, and continue ultrasonic disperse 2h,
The above-mentioned iron-based Prussian blue similar object positive pole powder (active material accounting 72%) of 0.5g is added thereto again, continues ultrasound
Gained mixture dispersion liquid is directly carried out on 0.45 μm of miillpore filter vacuum filtration film forming, washs drying, tear by 10min
Combination electrode film is compacted in the twin rollers being put under 20MPa pressure, obtains the flexible compound electrode of embodiment 5.
Comparative example 1
By 0.2g carbon nanotube in 20mL deionized water ultrasonic disperse 3h, by gained mixture dispersion liquid directly in micropore
It carries out vacuum filtration film forming on filter membrane, washs drying, combination electrode film of tearing, pictorial diagram is as shown in Fig. 6.From pictorial diagram
It can be seen that the composite membrane after vacuum filtration is dry obtains because making sqtructural adhesive without cellulosic material
It filters film and is very easy to fragmentation, flexible and mechanical strength is too low, cannot be used to do flexible battery electrode.
Comparative example 2
First take 0.05g Cellulose nanocrystal must in 20mL deionized water strength ultrasonic dissolution, then by carbon nanotube and fibre
It ties up the ratio that plain nano whisker is 5:1 in mass ratio to be added thereto, and continues ultrasonic disperse 3h, by gained dispersion liquid directly micro-
Vacuum filtration film forming is carried out on the filter membrane of hole, washs drying, and combination electrode film of tearing, combination electrode film thickness is 135 μm at this time, is put
Enter and be compacted in the twin rollers under 20MPa pressure, obtaining required 89 μm, (aluminum foil substrate combination electrode is to about 180 μ of thickness after roller
M) flexible compound electrode, pictorial diagram is as shown in Fig. 7, and scanning electron microscope sem figure is shown in attached drawing 8.It can be found that fiber material is added
After material, compound film electrode is just provided with preferable flexible and mechanical strength, can control flexibility by adjusting the ratio being added
With the quality of chemical property.
Above-mentioned flexible battery combination electrode preparation process can be found in as attached flow diagram shown in FIG. 1.Gained flexibility is multiple
It closes anode and lithium metal/sodium or uses the compound obtained hard carbon graphite of this method as flexible compound cathode, can be assembled into flexibility
Soft-package battery.In addition, particularly, it can also be (as shown in Figure 7) instead of metal aluminum foil or copper by 2 gained flexible current-collecting body of comparative example
Foil is directly coated in active material, conductive agent and binder above according to the slurry that proper proportion is formed, then carries out battery
Assembling.
Select the LiPF of 1M6With the NaClO of 1M4(EC/PC volume ratio 1:1) is respectively as the electrolysis of lithium/sodium-ion battery
Liquid, for microporous polypropylene membrane as diaphragm, lithium metal/sodium piece is assembled into the button cell of CR2032 as cathode, and uses blue electricity
Electrochemical property test is carried out in test cabinet (5V, 5mA).
1 flexible compound electrode assembling of embodiment can be shown in attached drawing at the first charge-discharge curve graph of lithium, sodium-ion battery respectively
9,10.By attached drawing 9 and attached drawing 10 it is found that recycling the specific volume that can release 157.2mAh/g for the first time to the cathode of lithium flexible electrode material
Amount recycles the specific capacity that can release 146.5mAh/g to the sodium cathode flexible electrode material for the first time.
2 flexible compound electrode assembling of embodiment can be shown in attached drawing at the first charge-discharge curve graph of lithium, sodium-ion battery respectively
11,12.By attached drawing 11 and attached drawing 12 it is found that recycling the ratio that can release 193.8mAh/g for the first time to the cathode of lithium flexible electrode material
Capacity recycles the specific capacity that can release 100.4mAh/g to the sodium cathode flexible electrode material for the first time.
From attached drawing 9~12 as it can be seen that flexible compound electrode lithium/sodium-ion battery electrochemistry made from the embodiment of the present invention
Can be more different, it is because of flexible composite FeF3·0.5H2O and FeF3·0.33H2The difference of O crystal structure itself, makes
It is embodied at the chemical property different as lithium/sodium-ion battery.
Claims (10)
1. a kind of preparation method of flexible compound electrode, it is characterised in that: the following steps are included:
1) cellulosic material is dissolved in solvent, adds carbon nanotube, be uniformly dispersed, obtain dispersion liquid；
2) it by the positive electrode of metal ion battery or negative electrode material investment dispersion liquid, is uniformly dispersed, filters film forming；
3) membrane material is washed, dry, compression moulding obtains flexible compound electrode.
2. a kind of preparation method of flexible compound electrode according to claim 1, it is characterised in that: in step 1), carbon is received
The mass ratio of mitron and cellulosic material is (1~9): 1.
3. a kind of preparation method of flexible compound electrode according to claim 1 or 2, it is characterised in that: fine in step 1)
Dimension cellulosic material be microcrystalline cellulose, Cellulose nanocrystal palpus, Nano bacteria cellulose, it is cellulose nano-fibrous at least one
Kind.
4. a kind of preparation method of flexible compound electrode according to claim 1 or 2, it is characterised in that: in step 1), carbon
The pipe range of nanotube is 10 μm~100 μm.
5. a kind of preparation method of flexible compound electrode according to claim 1, it is characterised in that: in step 1), solvent
For water, ethyl alcohol, acetone, ether, N-Methyl pyrrolidone, N,N-dimethylformamide, tetrahydrofuran, dimethyl sulfoxide, ion
At least one of liquid.
6. a kind of preparation method of flexible compound electrode according to claim 1 or 5, it is characterised in that: point of step 1)
It dissipates for ultrasonic disperse, the time of ultrasonic disperse is 0.5h~4h.
7. a kind of preparation method of flexible compound electrode according to claim 1, it is characterised in that: in step 2), metal
The positive electrode of ion battery is at least one of iron-based fluoride, Prussian blue similar object；The cathode of metal ion battery
Material is hard carbon, graphene, graphite, silicon-carbon, silicon-base oxide, Li4Ti5O12、Na3V2(PO4)3、Na2Ti6O13In at least one
Kind.
8. a kind of preparation method of flexible compound electrode according to claim 1 or claim 7, it is characterised in that: point of step 2)
It dissipates for ultrasonic disperse, the time of ultrasonic disperse is 1min~10min.
9. a kind of preparation method of flexible compound electrode according to claim 1, it is characterised in that: in step 3), compacting
It is shaped to be compacted in twin rollers with the pressure of 10MPa~120MPa.
10. a kind of flexible electrode of alkali metal-ion battery, it is characterised in that: for any one of the claim 1~9 preparation side
Flexible compound electrode made from method.
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| CN110581278A (en) * | 2019-09-24 | 2019-12-17 | 浙江农林大学 | Positive electrode material for flexible lithium ion battery, preparation method and application thereof, and flexible lithium ion battery |
| CN110600739A (en) * | 2019-08-22 | 2019-12-20 | 浙江工业大学 | Preparation method of metal lithium negative electrode protection layer material |
| CN111477854A (en) * | 2020-04-20 | 2020-07-31 | 董荣芳 | Composite nano material and preparation method and application thereof |
| CN111640945A (en) * | 2020-06-18 | 2020-09-08 | 合肥国轩高科动力能源有限公司 | Lithium ion battery anode slurry and preparation method thereof |
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| CN111653757A (en) * | 2020-04-26 | 2020-09-11 | 深圳瀚光科技有限公司 | Flexible self-supporting tellurium nanotube composite electrode, preparation method thereof and flexible battery |
| CN111653757B (en) * | 2020-04-26 | 2023-01-03 | 深圳瀚光科技有限公司 | Flexible self-supporting tellurium nanotube composite electrode, preparation method thereof and flexible battery |
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| CN111785898A (en) * | 2020-07-13 | 2020-10-16 | 南京林业大学 | Cellulose-based integrated zinc ion battery and preparation method thereof |
| CN111785898B (en) * | 2020-07-13 | 2022-12-16 | 南京林业大学 | Cellulose-based integrated zinc ion battery and preparation method thereof |
| CN112176771A (en) * | 2020-09-25 | 2021-01-05 | 柔电（武汉）科技有限公司 | Preparation method of lithium-philic carbon nanotube paper and preparation method of composite metal lithium cathode |
| CN113764202A (en) * | 2021-07-16 | 2021-12-07 | 西安交通大学 | Preparation method of supercapacitor electrode on film based on mixed cellulose ester |
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