CN109713261A - Carbonization silk fabric/transition metal oxide composite material and preparation method for flexible lithium ion battery cathode - Google Patents
Carbonization silk fabric/transition metal oxide composite material and preparation method for flexible lithium ion battery cathode Download PDFInfo
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Abstract
The present invention relates to a kind of carbonization silk fabric/transition metal oxide composite material and preparation methods for flexible lithium ion battery cathode, belong to energy storage system device material preparation technical field.Silk fabric is obtained carbonization silk fabric by carbonization by the present invention, is passing through low-kappa number, hydro-thermal or solvent thermal growth and subsequent anneal, obtains carbonization silk fabric/transition metal oxide composite material.Wherein, carbonization silk fabric has high conductivity, and transition metal oxide is evenly distributed on carbonization silk fabric with the pattern of nano wire, nanometer sheet, nano square.Obtained carbonization silk fabric/transition metal oxide has good chemical property and mechanical flexibility as negative electrode of lithium ion battery.
Description
Technical field
The present invention relates to a kind of energy storage system device material, in particular to a kind of carbon for flexible lithium ion battery cathode
Change silk fabric/transition metal oxide composite material and preparation method, belongs to energy storage system device material technology of preparing neck
Domain.
Background technique
Due to economical rapid development and continuous improvement of people's living standards, to portable electronic device and wearable electricity
The demand of sub- product increasingly increases, such as: Intelligent bracelet, flexible screen etc..Continuing to bring out for these flexible electronic products, needs
There is corresponding flexible energy storage device matching.Lithium ion battery is as secondary cell, compared to traditional lead-acid battery, ni-mh
Battery has the advantages such as high-energy density, high power density, memory-less effect, environmental-friendly, is increasingly becoming energy storage dress of new generation
It sets.Current commercial Li-ion batteries mainly use graphite as cathode, LiCoO2、LiNiO2、LiMn2O4Etc. slotting lithium compound
As anode, lithium salts is (such as: LiPF6、LiClO4、LiAsF6) organic solvent (such as: EC, PC, DMC) is dissolved in as electrolyte, poly- second
Alkene (PE), polypropylene (PP) are used as diaphragm.However, due to the presence of rigid electrode material, liquid organic electrolyte so that lithium from
Sub- battery cannot achieve flexibility, not be able to satisfy the demand of flexible electronic device.Realize that the flexibility of lithium ion battery is one and is
System property engineering, needs each component of battery to have flexibility.Wherein, liquid organic electrolyte and diaphragm can use flexible solid electricity
Matter is solved to replace, and flexible obtain of electrode material then needs from electrode this body structure design angle.
Carbon-based material has low cost, resourceful, high conductivity, good chemical stability, stabilizing mechanical performance and ring
The characteristics such as border close friend, are mainly used in lithium ion battery negative material.Wherein, carbon cloth, carbon paper, graphene paper etc. are emerging carbon-based
Material has good mechanical flexibility compared to the graphite carbon-based material as commercial Li-ion batteries cathode, can satisfy soft
The demand of property lithium ion battery.However, these carbon-based materials are but there is defect identical with graphite, i.e. energy density is low, nothing
Method meets the needs of extensive energy storage system, in addition, these carbon-based materials are mainly from fossil feedstock and non-renewable.And it is biological
Carbon-based material derived from matter, such as: silk, cotton, chitin, not only abundance is renewable, but also environmental-friendly pollution-free.
In various lithium ion battery negative materials, transition metal oxide (TMOs) has the specific capacity of 3 times of graphite
And the advantages such as low in cost, such as: ZnO, Co2O3、ZnCo2O4、NiCo2O4Deng, be expected to replace commercial graphite be applied to a new generation
Lithium ion battery.However, transition metal oxide is as negative electrode of lithium ion battery, but there is poorly conductive, lithium ion diffusion are slow
Slowly, the disadvantages of structural instability.It is compound with carbon-based material, conductivity not only can be improved, but also help to improve structure
Stability.
It, can be by transition gold to realize that lithium ion battery negative material has high-energy density, good mechanical advantage flexible
The carbon-based material for belonging to oxide and biomass derived is compound.Transition metal oxide improves the energy density of composite material, biology
Carbon-based material derived from matter improves whole mechanical flexibility.The composite material of this chemical property and mechanical flexibility and tool is in lithium
It has broad application prospects in ion battery cathode material.
Summary of the invention
It is compound that the present invention provides a kind of carbonization silk fabric/transition metal oxide for flexible lithium ion battery cathode
Material.
The present invention also provides carbonization silk fabric/transiting metal oxidations that flexible lithium ion battery cathode is used for described in one kind
The preparation method of object composite material.
The technical solution used to solve the technical problems of the present invention is that:
A kind of carbonization silk fabric/transition metal oxide composite material preparation side for flexible lithium ion battery cathode
Method, it is characterised in that method includes the following steps:
(1) preparation of carbonization silk fabric: under inert gas protection, silk fabric being carbonized at 600-1000 DEG C,
Obtain carbonization silk fabric;
(2) carbonization silk fabric pretreatment: the carbonization silk fabric that step (1) is obtained carries out sour processing, obtains pretreatment carbon
Change silk fabric;
(3) be carbonized silk fabric/transition metal oxide precursor body preparation: transition metal oxide precursor body salt is dissolved in solvent
In, hydro-thermal or solvent thermal reaction solution is made, then the pretreatment carbonization silk fabric that step (2) obtains is placed in hydro-thermal or solvent
In thermal response solution, hydro-thermal or solvent thermal reaction, time 6-16h are carried out at a temperature of 120-180 DEG C, are obtained carbonization silk and are knitted
Object/transition metal oxide precursor body;
(4) be carbonized silk fabric/transition metal oxide preparation: carbonization silk fabric/oxo transition metal that step (3) is obtained
Compound presoma is made annealing treatment, and annealing temperature is 300-500 DEG C, time 1-4h, obtains carbonization silk fabric/transition gold
Belong to oxide composite.
The method of the present invention preparation is simple, and obtained carbonization silk fabric can retain the institutional framework of fabric itself, and have
There is good electric conductivity;Transition metal oxide is evenly distributed on carbonization silk with the pattern of nano wire, nanometer sheet, nano square
On fabric;When obtained carbonization silk fabric/transition metal oxide composite material is as lithium ion battery negative material, have
Good chemical property and mechanical flexibility.
Preferably, the carburizing temperature in step (1) is 850-950 DEG C, carbonization time 2-3h, heating rate 2-4
℃/min。
Preferably, the acid that acid processing uses in step (2) is nitric acid, hydrochloric acid or sulfuric acid, sour treatment temperature is 80-140
DEG C, the acid processing time is 1-5h.It is further preferred that the acid processing time is 110 DEG C, the acid processing time is 2h.
Preferably, the transition metal oxide loaded on carbonization silk fabric in step (3), (4) is Dyadic transition gold
Belong to object or ternary transition metal oxide, binary transition metal object is selected from ZnO, Co2O3, NiO or Fe2O3;Ternary transition metal oxygen
Compound is selected from ZnCo2O4、NiCo2O4、FeCo2O4、NiMn2O4Or ZnFe2O4.Presoma used in general transition metal oxide
Salt is nitrate.
Preferably, the solvent in step (3) is in deionized water, dehydrated alcohol, N-N dimethylformamide or acetone
One or more combinations, hydro-thermal or solvent heat temperature are 170-180 DEG C, time 12-16h.
Preferably, the annealing heating rate in step (4) is 2-10 DEG C/min.It is further preferred that annealing temperature is
400 DEG C, time 2h, heating rate is 5 DEG C/min.
Preferably, the protective atmosphere is the mixing of one or more of argon gas, nitrogen, helium or neon, gas
Body flow velocity is 20-100sccm.
Preferably, the institutional framework of the silk fabric in step (1) is crepe de Chine, plain crepe-back satin, habotai, doupioni, tower
Husband's silk fabric, twill silk, georgette or dongfeng yarn.
A kind of carbonization silk fabric/transition metal oxide composite material for flexible lithium ion battery cathode, this is multiple
Condensation material is prepared by the preparation method.
The present invention first by silk fabric by carbonization obtains carbonization silk fabric, then, then will carbonization silk fabric into
Row low-kappa number, most afterwards through hydro-thermal or solvent heat and subsequent anneal on carbonization silk fabric carrying transition metal oxide,
Obtain carbonization silk fabric/transition metal oxide composite material.The material can be applied to the energy storage neck of flexible lithium ion battery
Domain has the following characteristics that
(1) present invention preparation is simple, easily-controlled reaction conditions and realization;
(2) carbonization silk fabric has satisfactory electrical conductivity and mechanical flexibility, can be used as flexible electronic device substrate;
It (3) can be by the type and hydro-thermal or solvent thermal reaction temperature, time of adjusting solvent, to control transiting metal oxidation
The pattern and load capacity of object;
(4) obtained carbonization silk fabric/transition metal oxide has good electrochemistry as negative electrode of lithium ion battery
Performance and mechanical flexibility.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram of carbonization silk fabric obtained by embodiment 1;
Fig. 2 is carbonization silk fabric/transition metal oxide composite material scanning electron microscope obtained by embodiment 2
Figure;
Fig. 3 is carbonization silk fabric/transition metal oxide composite material scanning electron microscope obtained by embodiment 3
Figure;
Fig. 4 is the chemical property figure of carbonization silk fabric obtained by embodiment 4;
Fig. 5 is carbonization silk fabric/transition metal oxide chemical property figure obtained by embodiment 4;
Fig. 6 is carbonization silk fabric/transition metal oxide chemical property figure obtained by embodiment 5.
Fig. 7 is carburizing temperature-resistivity properties figure of carbonization silk fabric obtained by embodiment 2-4.
Specific embodiment
Below by specific embodiment, technical scheme of the present invention will be further explained in detail.It should be appreciated that this hair
Bright implementation is not limited by the following examples, and the accommodation in any form made to the present invention and/or changed will all be fallen
Enter the scope of the present invention.
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, and all equipment and raw material etc. are equal
It is commercially available or the industry is common.
Embodiment 1
A kind of carbonization silk fabric/transition metal oxide composite material preparation side for flexible lithium ion battery cathode
Method, specific step is as follows for this method:
(1) preparation of carbonization silk fabric: the habotai silk fabric of one piece of 3cm × 4cm of clip is placed in tube furnace, 600
Be carbonized 3h in DEG C argon atmosphere, and heating rate is 2 DEG C/min, and argon gas flow velocity is 40sccm to get required carbonization silk fabric is arrived.
The shape appearance figure of carbonization silk fabric is shown in Fig. 1.
(2) carbonization silk fabric pretreatment: gained carbonization silk fabric in (1) is placed in 6M HCl solution, at 100 DEG C
Lower acid processing 2h after natural cooling, takes out carbonization silk fabric, is washed repeatedly 3 times, 80 DEG C in deionized water and dehydrated alcohol
Dry 12h obtains pretreatment carbonization silk fabric.
(3) be carbonized silk fabric/transition metal oxide precursor body preparation: firstly, accurately weighing 1m with assay balance
mol Zn(NO3)2·6H2O, 1m mol urea, 1 m mol NH4F is dissolved in 50 mL deionized waters, and 15min is stirred by ultrasonic,
Obtain hydrothermal solution;Then, gained pretreatment carbonization silk fabric in (2) is placed in hydrothermal solution, the hydro-thermal at 120 DEG C
6h;Finally, taking out carbonization silk fabric to natural cooling, with washing repeatedly in deionized water and dehydrated alcohol 3 times, 80 DEG C dry
Dry 12h obtains carbonization silk fabric/transition metal oxide precursor body.
(4) be carbonized silk fabric/transition metal oxide preparation: by gained carbonization silk fabric/oxo transition metal in (3)
Compound presoma is placed in tube furnace, and anneal 1h in 300 DEG C of argon atmospheres, and heating rate is 2 DEG C/min, and argon gas flow velocity is
40sccm to get to carbonization silk fabric/transition metal oxide composite material.
Embodiment 2
A kind of carbonization silk fabric/transition metal oxide composite material preparation side for flexible lithium ion battery cathode
Method, specific step is as follows for this method:
(1) preparation of carbonization silk fabric: the crepe de Chine silk fabric of one piece of 3cm × 4cm of clip is placed in tube furnace, at 700 DEG C
Be carbonized 4h in neon atmosphere, heating rate be 5 DEG C/min, neon flow velocity be 40sccm to get arrive required carbonization silk fabric.
(2) carbonization silk fabric pretreatment: gained carbonization silk fabric in (1) is placed in 4M HCl solution, at 120 DEG C
Lower acid processing 4h after natural cooling, takes out carbonization silk fabric, is washed repeatedly 3 times, 80 DEG C in deionized water and dehydrated alcohol
Dry 12h obtains pretreatment carbonization silk fabric.
(3) be carbonized silk fabric/transition metal oxide precursor body preparation: firstly, accurately weighing 1m with assay balance
mol Co(NO3)3·6H2O, 1m mol urea, 1 m mol NH4F is dissolved in 50 mL dehydrated alcohols, and 15min is stirred by ultrasonic,
Obtain solvent hot solution;Then, gained pretreatment carbonization silk fabric in (2) is placed in solvent hot solution, it is molten at 100 DEG C
The hot 8h of agent;Finally, to natural cooling, carbonization silk fabric is taken out, with washing repeatedly 3 times in deionized water and dehydrated alcohol, 80
DEG C dry 12h, obtains carbonization silk fabric/transition metal oxide precursor body.
(4) be carbonized silk fabric/transition metal oxide preparation: by gained carbonization silk fabric/oxo transition metal in (3)
Compound presoma is placed in tube furnace, and anneal 2h in 350 DEG C of neon atmosphere, and heating rate is 5 DEG C/min, and neon flow velocity is
40sccm to get to carbonization silk fabric/transition metal oxide composite material.Be carbonized silk fabric/transition metal oxide
The shape appearance figure of composite material is shown in Fig. 2.
Embodiment 3
A kind of carbonization silk fabric/transition metal oxide composite material preparation side for flexible lithium ion battery cathode
Method, specific step is as follows for this method:
(1) preparation of carbonization silk fabric: the georgette silk fabric of one piece of 3cm × 4cm of clip is placed in tube furnace, 800
Be carbonized 4h in DEG C nitrogen atmosphere, and heating rate is 6 DEG C/min, and nitrogen flow rate is 80sccm to get required carbonization silk fabric is arrived.
(2) gained carbonization silk fabric in (1) carbonization silk fabric pretreatment: is placed in 5M HNO3In solution, 110
Acid processing 2h at DEG C after natural cooling, takes out carbonization silk fabric, with washing repeatedly 3 times in deionized water and dehydrated alcohol, 80
DEG C dry 12h, obtains pretreatment carbonization silk fabric.
(3) be carbonized silk fabric/transition metal oxide precursor body preparation: firstly, accurately weighing 1m with assay balance
mol Zn(NO3)2·6H2O, 2m mol Co (NO3)3·6H2O, 1m mol urea, 1 m mol NH4F is dissolved in 50 mL mixing
In solution (deionized water: N-N dimethylformamide=2:3, volume ratio), 15min is stirred by ultrasonic, obtains solvent hot solution;So
Afterwards, gained pretreatment carbonization silk fabric in (2) is placed in solvent hot solution, the solvent heat 12h at 180 DEG C;Finally, to certainly
It is so cooling, carbonization silk fabric is taken out, with washing repeatedly in deionized water and dehydrated alcohol 3 times, 80 DEG C of dry 12h obtain carbon
Change silk fabric/transition metal oxide precursor body.
(4) be carbonized silk fabric/transition metal oxide preparation: by gained carbonization silk fabric/oxo transition metal in (3)
Compound presoma is placed in tube furnace, and anneal 4h in 400 DEG C of nitrogen atmospheres, and heating rate is 6 DEG C/min, and nitrogen flow rate is
80sccm to get to carbonization silk fabric/transition metal oxide composite material.Be carbonized silk fabric/transition metal oxide
The shape appearance figure of composite material is shown in Fig. 3.
By Fig. 2 and Fig. 3 it is found that carbonization silk fabric loads different types of transition metal oxide, obtained surface
Pattern is also different.
Embodiment 4
A kind of carbonization silk fabric/transition metal oxide composite material preparation side for flexible lithium ion battery cathode
Method, specific step is as follows for this method:
(1) preparation of carbonization silk fabric: the twill silk silk fabric of one piece of 3cm × 4cm of clip is placed in tube furnace, 900
Be carbonized 8h in DEG C mixed gas (argon gas: hydrogen=2:3, volume ratio) atmosphere, and heating rate is that 5 DEG C/min gas flow rate is
100sccm to get arrive required carbonization silk fabric.The chemical property of carbonization silk fabric is shown in Fig. 4.
(2) gained carbonization silk fabric in (1) carbonization silk fabric pretreatment: is placed in 5M HNO3In solution, 130
Acid processing 2h at DEG C after natural cooling, takes out carbonization silk fabric, with washing repeatedly 3 times in deionized water and dehydrated alcohol, 80
DEG C dry 12h, obtains pretreatment carbonization silk fabric.
(3) be carbonized silk fabric/transition metal oxide precursor body preparation: firstly, accurately weighing 1m with assay balance
mol Ni(NO3)2·6H2O, 2m mol Co (NO3)3·6H2O, 1m mol urea, 1 m mol NH4F is dissolved in 50 mL mixing
In solution (deionized water: dehydrated alcohol=1:1, volume ratio), 15min is stirred by ultrasonic, obtains solvent hot solution;Then, by (2)
Middle gained pretreatment carbonization silk fabric is placed in solvent hot solution, the solvent heat 12h at 150 DEG C;Finally, to natural cooling,
Carbonization silk fabric is taken out, with being washed repeatedly in deionized water and dehydrated alcohol 3 times, 80 DEG C of dry 12h, carbonization silk is obtained and knits
Object/transition metal oxide precursor body.
(4) be carbonized silk fabric/transition metal oxide preparation: by gained carbonization silk fabric/oxo transition metal in (3)
Compound presoma is placed in tube furnace, and anneal 2h in 400 DEG C of nitrogen atmospheres, and heating rate is 5 DEG C/min, and nitrogen flow rate is
100sccm to get to carbonization silk fabric/transition metal oxide composite material.
The present embodiment carbonization silk fabric/transition metal oxide chemical property obtained is shown in Fig. 5.
By Fig. 4 and Fig. 5 it is found that charging and discharging capacity obviously mentions after carbonization silk fabric carrying transition metal oxide
Height, this high theoretical capacity for being attributed to transition metal oxide improve the overall performance of composite material.
Embodiment 5
A kind of carbonization silk fabric/transition metal oxide composite material preparation side for flexible lithium ion battery cathode
Method, specific step is as follows for this method:
(1) preparation of carbonization silk fabric: the taffeta silk fabric of one piece of 3cm × 4cm of clip is placed in tube furnace,
Be carbonized 10h in 1000 DEG C of mixed gas (nitrogen: helium: hydrogen=2:2:1, volume ratio) atmosphere, and heating rate is 10 DEG C/min,
Gas flow rate be 100sccm to get arrive required carbonization silk fabric.
(2) gained carbonization silk fabric in (1) carbonization silk fabric pretreatment: is placed in 5M H2SO4In solution, 140
Acid processing 5h at DEG C after natural cooling, takes out carbonization silk fabric, with washing repeatedly 3 times in deionized water and dehydrated alcohol, 80
DEG C dry 12h, obtains pretreatment carbonization silk fabric.
(3) be carbonized silk fabric/transition metal oxide precursor body preparation: firstly, accurately weighing 1m with assay balance
mol Zn(NO3)2·6H2O, 2m mol Fe (NO3)3·9H2O, 1m mol urea, 1 m mol NH4F is dissolved in 50 mL acetone
In, 15min is stirred by ultrasonic, obtains solvent hot solution;Then, gained pretreatment carbonization silk fabric in (2) is placed in solvent heat
In solution, the solvent heat 16h at 180 DEG C;Finally, carbonization silk fabric is taken out, with deionized water and anhydrous second to natural cooling
It is washed repeatedly in alcohol 3 times, 80 DEG C of dry 12h, obtains carbonization silk fabric/transition metal oxide precursor body.
(4) be carbonized silk fabric/transition metal oxide preparation: by gained carbonization silk fabric/oxo transition metal in (3)
Compound presoma is placed in tube furnace, and anneal 4h in 500 DEG C of argon atmospheres, and heating rate is 10 DEG C/min, and argon gas flow velocity is
100sccm to get to carbonization silk fabric/transition metal oxide composite material.
The present embodiment carbonization silk fabric/transition metal oxide chemical property obtained is shown in Fig. 6.
By Fig. 5 and Fig. 6 it is found that carbonization silk fabric loads different types of transition metal oxide, chemical property
It is different.
The scanning electron microscope diagram of carbonization silk fabric is as shown in Figure 1, the SEM by Fig. 1 is swept obtained by embodiment 1
Electron-microscopic analysis discovery is retouched, carbonization silk fabric prepared by embodiment 1 remains the institutional framework of original silk fabric, and
Fiber surface is smooth, and accurate, about 10 μm of silk fiber diameter of carbonization is arranged between fiber.
Be carbonized silk fabric/transition metal oxide composite material scanning electron microscope obtained by embodiment 2 and 3
Figure is as shown in Figures 2 and 3 respectively, by the SEM scanning electron microscope comparative observation to Fig. 2 and Fig. 3, when carbonization silk fabric into
When row solvent thermal reaction, when the type and reaction condition difference of solvent, the transition metal oxide of different-shape can be obtained,
Transition metal oxide (Co in middle embodiment 22O3) in the form of nano square, it is evenly distributed on carbonization silk fabric, and
Transition metal oxide (ZnCo in embodiment 32O4) in the form of nano wire, it is evenly distributed on carbonization silk fabric.
To be carbonized silk fabric and carbonization silk fabric/transition metal oxide composite material progress electricity in embodiment 4
Chemical property finds that pure carbonization silk fabric is in 100mA g when testing-1Current density under circulation 100 circle, have 85.2mAh
g-1Specific capacity, and after carrying transition metal oxide, specific capacity is promoted to 778mAh g-1, and coulombic efficiency is greater than 99%,
The chemical property of raising is attributed to the high theoretical capacity of transition metal oxide and the carbonization good conductive network of silk fabric.
Carbonization silk fabric/transition metal oxide composite material in embodiment 5 is in 100mAh g-1Current density under recycle 200
Circle has 657mAh g-1Specific capacity, this shows when the transition metal oxide type difference of load, obtained compound
There is also differences for the chemical property of material.
The resistivity of carbonization silk fabric in embodiment 2-4 is compared discovery, carbonization silk fabric electricity at 900 DEG C
Resistance rate is minimum, is more conducive to the conduction of the electronics in lithium-ion battery system.
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form
Limitation, there are also other variations and modifications on the premise of not exceeding the technical scheme recorded in the claims.
Claims (10)
1. a kind of carbonization silk fabric/transition metal oxide composite material preparation side for flexible lithium ion battery cathode
Method, it is characterised in that method includes the following steps:
(1) preparation of carbonization silk fabric: under inert gas protection, silk fabric being carbonized at 600-1000 DEG C,
Obtain carbonization silk fabric;
(2) carbonization silk fabric pretreatment: the carbonization silk fabric that step (1) is obtained carries out sour processing, obtains pretreatment carbon
Change silk fabric;
(3) be carbonized silk fabric/transition metal oxide precursor body preparation: transition metal oxide precursor body salt is dissolved in solvent
In, hydro-thermal or solvent thermal reaction solution is made, then the pretreatment carbonization silk fabric that step (2) obtains is placed in hydro-thermal or solvent
In thermal response solution, hydro-thermal or solvent thermal reaction, time 6-16h are carried out at a temperature of 120-180 DEG C, are obtained carbonization silk and are knitted
Object/transition metal oxide precursor body;
(4) be carbonized silk fabric/transition metal oxide preparation: carbonization silk fabric/oxo transition metal that step (3) is obtained
Compound presoma is made annealing treatment, and annealing temperature is 300-500 DEG C, time 1-4h, obtains carbonization silk fabric/transition gold
Belong to oxide composite.
2. preparation method according to claim 1, it is characterised in that: the carburizing temperature in step (1) is 850-950 DEG C,
Carbonization time is 2-3h, and heating rate is 2-4 DEG C/min.
3. preparation method according to claim 1, it is characterised in that: the acid that acid processing uses in step (2) is nitric acid, salt
Acid or sulfuric acid, sour treatment temperature are 80-140 DEG C, and the acid processing time is 1-5h.
4. preparation method according to claim 1, it is characterised in that: loaded on carbonization silk fabric in step (3), (4)
Transition metal oxide be binary transition metal object or ternary transition metal oxide, binary transition metal object be selected from ZnO,
Co2O3, NiO or Fe2O3;Ternary transition metal oxide is selected from ZnCo2O4、NiCo2O4、FeCo2O4、NiMn2O4Or ZnFe2O4。
5. preparation method according to claim 1, it is characterised in that: the solvent in step (3) is deionized water, anhydrous second
One of alcohol, N-N dimethylformamide or acetone or multiple combinations, hydro-thermal or solvent heat temperature are 170-180 DEG C, and the time is
12-16h。
6. preparation method according to claim 1, it is characterised in that: annealing heating rate in step (4) is 2-10 DEG C/
min。
7. preparation method according to claim 1, it is characterised in that: the annealing temperature in step (4) is 400 DEG C, the time
For 2h, heating rate is 5 DEG C/min.
8. preparation method according to claim 1, it is characterised in that: the protective atmosphere be argon gas, nitrogen, helium or
The mixing of one or more of neon, gas flow rate 20-100sccm.
9. preparation method according to claim 1, it is characterised in that: the institutional framework of the silk fabric in step (1) is
Crepe de Chine, plain crepe-back satin, habotai, doupioni, taffeta, twill silk, georgette or dongfeng yarn.
10. a kind of carbonization silk fabric/transition metal oxide composite material for flexible lithium ion battery cathode, this is compound
Material is prepared by preparation method described in claim 1.
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