CN109256528A - LiFePO4-bacteria cellulose-graphene composite material and its preparation method and application - Google Patents
LiFePO4-bacteria cellulose-graphene composite material and its preparation method and application Download PDFInfo
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Abstract
The present invention discloses LiFePO4-bacteria cellulose-graphene composite material and its preparation method and application; it is mixed using LiFePO4, bacteria cellulose and graphene as raw material; and heated up and filtered film forming; carbonization treatment is carried out in inert protective gas and hydrogen atmosphere again, forms composite material.It is applied as anode material for lithium-ion batteries.The material shows splendid cycle performance and compared with high charge-discharge capacity, and itself has excellent flexibility and self-supporting.
Description
Technical field
The invention belongs to technical field of composite materials, more particularly, will be by utilizing LiFePO4, bacteria cellulose
And graphene as raw material preparation flexibility, toughness, high discharge capacity anode material for lithium-ion batteries, thus integrated for preparation
Change flexible battery and anode support is provided, prepared target electrode would be possible to be widely used in fabric and mechanical environment is changeable
Under conditions of, all there is potential application prospect in many fields such as aerospace.
Background technique
The people of attention with to(for) environment and energy problem, more and more concerns concentrate on possessing it is efficient, renewable,
On the emerging natural energy resources such as wind energy, solar energy and the tide energy of advantages of environment protection.However it is not difficult to find that above-mentioned natural energy resources
It cannot achieve continuous action, large-scale commercial is used if thinking, becomes the core pillar in new energy structure, then
Must have can be with the matched energy storage device of its characteristic institute.Battery is a kind of dress that chemical energy can be directly changed into electric energy
Set, due to its higher energy utilization rate and simple working principle, undoubtedly become today's society most and have researching value and
The energy storage device of utility value.At the same time, the high speed development of electronic information technology neighborhood and related discipline has been greatly facilitated electricity
The development process of sub- instrument and equipment miniaturization, in order to meet constantly harsh common requirements, market is gradually to the performance product of power supply
More stringent requirements are proposed for matter and cost budgeting.In addition to this, as the environment of global facing, Pressure on Energy increasingly increase
Greatly, after electric car is by research and development of constantly bringing forth new ideas, update, orthodox car will be substituted gradually to thoroughly solve by fossil energy
Source consumes the inexorable trend that brought a series of problems has become era development, wherein the battery system for providing power is exactly a left side
The core link of right Development of Electric Vehicles process, based on this research background, probe into as early as possible, research and develop it is inexpensive, environmental-friendly, comprehensive
The high-specific energy battery of function admirable becomes the task of top priority.
Goodenough et al. was considered as LiFePO4 (LiFePO4) in 1997 as lithium ion cell positive for the first time
Material, due to the material have raw material sources enrich, have compared with long circulation life, charge/discharge landing flat (3.4V vs.Li+/
Li) and possess the excellent properties such as higher theoretical capacity (170m Ahg-1), just got the attention once proposition.Phosphorus
Sour iron lithium plays the effect of cannot be neglected as a kind of very promising positive electrode, in field of batteries.Bacterium is fine
Dimension element has received widespread attention as natural polymer because of its unique physical and chemical performance, and the spy to its performance and application
Study carefully and has obtained certain achievement at present.Graphene is a kind of two-dimentional carbon nanomaterial with monoatomic thickness, itself is had excellent
Electricity, optics, calorifics and mechanical property, and more than other carbon-based materials (including: carbon nanotube, carbon fiber, graphite etc.)
Big specific surface area, therefore, it has become the ideal materials for preparing a variety of high-strength structure materials, catalyst and energy device.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide LiFePO4-bacteria cellulose-graphene is multiple
Condensation material and its preparation method and application, under the conditions of Different Preparation the microscopic appearance of acquired sample, structure and at
It is grouped as, in addition, sample film is further assembled button cell as anode material for lithium-ion batteries and tests its electrification
Performance is learned, has probed into Different Preparation to LiFePO4/bacterial cellulose/graphene composite material physical property and electrification
Learn the influence of performance.
Technical purpose of the invention is achieved by following technical proposals:
LiFePO4-bacteria cellulose-graphene composite material and preparation method thereof, with lithium phosphate, citric acid and oxygen
The mixed solution of graphite alkene is added in the mixed solution of bacteria cellulose and ferrous sulfate, through hydro-thermal reaction and carbonization treatment
After obtain LiFePO4-bacteria cellulose-graphene composite material, the quality of LiFePO4, bacteria cellulose and graphene
Than for (1-5): (1-2): (1-2) carry out as steps described below:
Step 1, FeSO47H2O, Li3PO4 and citric acid are weighed by the mass ratio of the material 3:3:1, is molten with deionized water
Li3PO4 and citric acid are uniformly mixed and are added graphene oxide by agent, and ultrasonic disperse is uniform, form the first solution；
In step 1, Li3PO4 and citric acid are mixed in beaker, dissolved, then solution is ultrasonically treated,
Solution is in colorless and transparent sufficiently after reaction, is ultrasonically treated to solution, and solution is in colorless and transparent sufficiently after reaction.
Step 2, bacteria cellulose has been added in the sufficiently aqueous solution of dissolution dispersion FeSO47H2O, height is carried out to it
Speed cutting decentralized processing and ultrasonic disperse form bacteria cellulose-FeSO47H2O and disperse solution, i.e. the second solution；
Step 3, the first solution is added drop-wise in the second solution and forms finely dispersed LiFePO4-bacteria cellulose-
Graphene composite dispersion liquid, and be fitted into hydrothermal reaction kettle, from 20-25 degrees Celsius of the room temperature heating rates with 8-12 DEG C/min
It is warming up to 150-200 DEG C and keeps the temperature 4-8h and reacted, be filtered by vacuum after hydro-thermal reaction and sample is filtered into film forming to get arriving
LiFePO4-bacteria cellulose-graphene composite material film is simultaneously freeze-dried；
Step 4, LiFePO4-bacteria cellulose-graphene composite material film step 3 obtained is transferred to tubular type
Carbonizing reduction processing is carried out under argon gas stream and hydrogen stream protection in furnace, controls argon gas stream and hydrogen stream in entire carbonisation
Flow velocity, argon gas flow velocity are 120-180mL/min, hydrogen flow rate 10-20mL/min, the heating curve setting of tube furnace are as follows: from
20-25 degrees Celsius of the room temperature heating rates with 2-5 DEG C/min are heated to 300-350 DEG C, the heated at constant temperature 1-2 at the temperature
Hour, 600-650 DEG C hereafter are heated to the heating rate of 4-8 DEG C/min, and heated at constant temperature 1.5-2.5 is small at the temperature
When, to guarantee that sample can be realized carbonization processing, 20-25 degrees Celsius of last cooled to room temperature obtains target production
Object: LiFePO4-bacteria cellulose-graphene composite material.
In the technical solution of the present invention, the mass ratio of LiFePO4, bacteria cellulose and graphene is (3-5): (1-
2): (1-2), bacteria cellulose and graphene preferably wait mass ratioes.
In step 3,180-200 DEG C is warming up to from 20-25 degrees Celsius of the room temperature heating rates with 8-12 DEG C/min and protect
Warm 6-8h is reacted.
In step 3, using being at the uniform velocity added dropwise, rate of addition is 5-10ml per minute.
In step 4, the flow velocity of argon gas stream and hydrogen stream in entire carbonisation is controlled, argon gas flow velocity is 120-160mL/
Min, hydrogen flow rate 15-20mL/min, the heating curve setting of tube furnace are as follows: from 20-25 degrees Celsius of room temperature with 2-5 DEG C/
The heating rate of min is heated to 320-350 DEG C, the heated at constant temperature 1-1.5 hours at the temperature, hereafter with 4-8 DEG C/min's
Heating rate is heated to 620-650 DEG C, and heated at constant temperature 2-2.5 hours at the temperature, to guarantee that sample can be realized
Full carbonization treatment, 20-25 degrees Celsius of last cooled to room temperature.
The present invention is successfully prepared LiFePO4/bacterial cellulose/graphene composite material, and is applied as lithium ion
Cell positive material.The material shows splendid cycle performance and compared with high charge-discharge capacity, and itself has excellent flexibility
And self-supporting.
Detailed description of the invention
Fig. 1 is LiFePO4 of the present invention/bacterial cellulose/graphene composite material preparation process flow diagram.
Fig. 2 is LiFePO4 of the present invention/bacterial cellulose/graphene composite material sample stereoscan photograph.
Fig. 3 is LiFePO4 of the present invention/bacterial cellulose/graphene composite material sample transmission electron microscope photo.
Fig. 4 be in the present invention after 600 DEG C of high temperature cabonizations LiFePO4/bacterial cellulose/graphene composite material sample
CV curve test.
Fig. 5 be in the present invention after 600 DEG C of high temperature cabonizations LiFePO4/bacterial cellulose/graphene composite material sample
Charging and discharging curve.
Fig. 6 be in the present invention after 600 DEG C of high temperature cabonizations LiFePO4/bacterial cellulose/graphene composite material sample
Cycle performance figure.
Specific embodiment
Technical solution of the present invention is illustrated below by way of specific embodiment.
Bacteria cellulose (Bacterial cellulose, BC, i.e. biological fiber) refers at different conditions, by acetic acid
Pseudomonas (Acetobacter), Agrobacterium (Agrobacterium), rhizobium (Rhizobium) and Sarcina
(Sarcina) general designation of the cellulose of certain Microbe synthesis in such as；It will be purchased from Hainan Guangyu Biotechnology Co., Ltd.
(a kind of high-molecular compound generated by gluconate pyracetobacillus is fermented generation bacteria cellulose by the natural strain of nature
Fiber, be the smallest natural fiber in nature, fibre diameter size is about 20~100nm, and netted pore structure is big
Small about 0.5~1.0um) it is pre-processed, it is filtered after high speed machine cutting dispersion in deionized water, washing sample is straight repeatedly
To its pH stable in neutrality, kept dry is spare.
Graphene oxide is prepared by raw material of graphite, the specific steps are as follows:
(1) it the low-temp reaction stage of graphene oxide: measures the 20mL concentrated sulfuric acid and pours into beaker, beaker is put into ice bath cooling
To 3 DEG C hereinafter, weighing 0.5g graphite powder and 0.2g sodium nitrate is put into beaker, 1h is slowly added to 2.5g potassium permanganate later, controls
Temperature is no more than 8 DEG C, reaction time 1.5h.
(2) the medium temperature stage of reaction of graphene oxide: beaker is moved to thermostat water bath, bath temperature is controlled in 35-40
DEG C reaction 0.5h, be kept stirring 100-150 turns/min.
(3) the pyroreaction stage of graphene oxide: being slowly added to the deionized water of 70mL in gained mixed liquor, control
During which 90 DEG C of reaction 0.5h of mixeding liquid temperature keep being slightly agitated for 100-150 turns/min.
(4) 50mL deionized water stopped reaction is added after pyroreaction, the hydrogen peroxide (percentage by volume of 10mL is added
The aqueous hydrogen peroxide solution of 30vol%) the 30mL hydrochloric acid (hydrogen chloride of percentage by volume 10vol% is added after reacting 10min
Aqueous solution).The excessive acid of low-speed centrifugal washing removal and by-product, the graphite oxide being in neutrality after washing is dispersed in water,
Using ultrasonic 30-60min of peel sample, after 20min is centrifuged under 2000rmin-1 revolving speed, upper liquid is to aoxidize
Graphene suspension takes out sample and saves backup.
FeSO47H2O, Li3PO4 and citric acid are weighed by the mass ratio of the material 3:3:1, using deionized water as solvent, configuration
Solution.When being fed intake, fed intake according to the feed ratio of LiFePO4, bacteria cellulose and graphene, i.e., LiFePO4,
The mass ratio of bacteria cellulose and graphene is (1-5): (1-2): the matter such as (1-2), bacteria cellulose and graphene are preferably
Amount ratio；According to graphene dosage and graphene oxide turbid liquid concentration, the graphene oxide suspension of preparation is selected to feed intake；
According to bacteria cellulose dosage, bacteria cellulose feeds intake when prepared by selection；According to LiFePO4 dosage, when prepared by selection
The dosage of FeSO47H2O, Li3PO4 and citric acid, three's the mass ratio of the material are 3:3:1.
Example 1
(1) firstly, Li3PO4 and citric acid are mixed in No. 1 beaker, dissolved, solution is ultrasonically treated,
Solution is in colorless and transparent sufficiently after reaction.Backward solution in be added graphene oxide suspension, to mixed solution carry out ultrasound
Processing is until mixed solution is ready to complete in No. 2 beakers.No. 2 beakers separately are taken, will be added by pretreated bacteria cellulose
Enter in the FeSO47H2O aqueous solution sufficiently dissolved, high-speed cutting decentralized processing carried out to it, need to equally control its revolving speed by
Lower starting speed gradually increases, and obtains bacteria cellulose/FeSO47H2O dispersion solution；LiFePO4, bacteria cellulose
Mass ratio with graphene is 1:1:1；
(2) hydro-thermal will be packed by the LiFePO4/bacteria cellulose/graphene composite dispersion liquid for sufficiently reacting and dispersing
In reaction kettle, set Muffle furnace heating curve: from 20-25 degrees Celsius of room temperature, heating temperature is 150 DEG C, soaking time 4h,
Heating rate be 8 DEG C/min, after the sample of hydro-thermal process to be done is cooled to room temperature, using vacuum filtration pump by sample filter at
Obtained sample is placed in freeze-drying to get LiFePO4/bacterial cellulose/graphene composite material film has been arrived by film
It is freeze-dried in machine；
(3) by the clean and dry scissors of the LiFePO4 of above-mentioned acquisition/bacterial cellulose/graphene composite material film
Thin rounded flakes are cut into, button cell internal diameter is dimensioned slightly smaller than.It is transferred into tube furnace later in argon gas stream and hydrogen
Carbonization treatment is carried out under air-flow protection, controlling the flow velocity of argon gas stream and hydrogen stream in entire carbonisation, (argon gas flow velocity is
120mL/min, hydrogen flow rate 10mL/min).The heating curve of tube furnace is set: by thin rounded flakes sample first with 2 DEG C/min
Heating rate be heated to 300 DEG C, 1 hour of heated at constant temperature, is hereafter heated to the heating rate of 4 DEG C/min at the temperature
600 DEG C, and 1.5 hours of heated at constant temperature at the temperature, to guarantee that sample can be realized carbonization processing.It is last natural
It is cooled to room temperature 20-25 degrees Celsius and obtains target product: LiFePO4/bacterial cellulose/graphene composite material；
It (4) is button by the LiFePO4 Jing Guo carbonization treatment/bacterial cellulose/graphene composite material film sample assembly
Formula battery.Its specific assembly method are as follows: according to button cell structure chart in the glove box full of argon gas, successively by button electricity
Pond lower cover, spring leaf, lithium piece, diaphragm, the experiment pole piece (LiFePO4 of preparation/bacterial cellulose/graphene composite material film
Sample, as cell positive material carry out using) assembled, while needing constantly to add electrolyte LB335C in this process,
Button cell upper cover pressurization is finally completed to the assembling of button cell.(notes: must be used during assembled battery exhausted
The tools such as edge tweezers, to guarantee that button cell will not influence chemical property because operating short circuit).Use model CT2001A
The electric battery test system of indigo plant and the electrochemical workstation of model CHI602E electricity is carried out to the above-mentioned button cell being completed
The test of chemical property.
LiFePO4/bacterial cellulose/graphene composite material preparation process in example 1 is as shown in Figure 1.
LiFePO4/bacterial cellulose/graphene composite material sample stereoscan photograph in example 1 is (such as Fig. 2 institute
Show), from (a) it is observed that experiment preparation LiFePO4/bacterial cellulose/graphene composite material be big lamella knot
Structure is uniformly spread in the visual field, and lamella framework is then constructed by the graphene oxide layer for possessing huge specific surface area.At (b)
In can be clearly seen that, LiFePO4/bacterial cellulose/graphene composite material " point-line-surface " design feature: ferric phosphate
Lithium particle is uniformly distributed on graphene sheet layer, meanwhile, it between lamella and lamella, is connected, has been finally constituted this by fiber
Special three-dimensional multi-slice interconnection architecture.It can be seen that the fiber and small range that are attached on graphene sheet layer in (c)
The lithium iron phosphate particles of reunion, this illustrates three kinds of core starting monomers (lithium iron phosphate particles, graphene sheet layer and the fibre that is chopped
Dimension) it can be effectively compound each other and be connected with each other and further enhance the structural stability of composite material, improve the electricity of composite material
Subconductivity rate and ion diffusion rates enhance battery comprehensive performance.
LiFePO4/bacterial cellulose/graphene composite material sample transmission electron microscope photo in example 1 is (such as Fig. 3 institute
Show), it can be seen that sample is gradually loose in the fiber part of its network-like structure after 600 DEG C of carbonizations, while fibre diameter
It reduces.
LiFePO4/bacterial cellulose/graphene composite material sample CV is bent after 600 DEG C of high temperature cabonizations in example 1
Line tests (as shown in Figure 4), reflects the CV scanning curve that the composite material of experiment preparation is recycled in the first two, CV curve in figure
Scanning speed be 0.5mV.s-1
LiFePO4/bacterial cellulose/graphene composite material sample charge and discharge after 600 DEG C of high temperature cabonizations in example 1
Electric curve (as shown in Figure 5), it is shown that the composite wood after 600 DEG C of carbonizations in the section 2-4.5V, under 20mA/g current density
Expect the preceding curve of constant-current discharge three times and cycle performance of sample.It can be clearly seen that from figure, it is fine in the LiFePO4/bacterium
Dimension element/graphene composite material in discharge process, will appear apparent discharge platform in 3.5V or so, in second later for the first time
In secondary and third time circulation, discharge platform, which is stablized, to be overlapped.It additionally can be seen that LiFePO4/bacteria cellulose of experiment preparation/
The capacity that graphene composite material discharges for the first time under the current density of 20mA/g is 122mAh/g.When circulation continues,
Second and third secondary charging and discharging curve is almost overlapped, this absolutely proves the button cell of experiment assembling, and battery capacity is continuous
It tends towards stability after circulation.
LiFePO4/bacterial cellulose/graphene composite material sample circulation after 600 DEG C of high temperature cabonizations in example 1
Performance (as shown in Figure 6), after 40 circulations, the reversible capacity of composite sample is still maintained after 600 DEG C of carbonizations
In 120mAh/g or more.Meanwhile composite sample is remaining to be kept close to 1 coulombic efficiency after 40 groups of circulations, card
The anode that this composite material is prepared, which is illustrated, has excellent cycle performance.
Example 2
(1) firstly, Li3PO4 and citric acid are mixed in No. 1 beaker, dissolved, solution is ultrasonically treated,
Solution is in colorless and transparent sufficiently after reaction.Backward solution in be added graphene oxide suspension, to mixed solution carry out ultrasound
Processing is until mixed solution is ready to complete in No. 2 beakers.No. 2 beakers separately are taken, will be added by pretreated bacteria cellulose
Enter in the FeSO47H2O aqueous solution sufficiently dissolved, high-speed cutting decentralized processing carried out to it, need to equally control its revolving speed by
Lower starting speed gradually increases, and obtains bacteria cellulose/FeSO47H2O dispersion solution；LiFePO4, bacteria cellulose
Mass ratio with graphene is 5:1:1；
(2) hydro-thermal will be packed by the LiFePO4/bacteria cellulose/graphene composite dispersion liquid for sufficiently reacting and dispersing
In reaction kettle, set Muffle furnace heating curve: from 20-25 degrees Celsius of room temperature, heating temperature is 150 DEG C, soaking time 8h,
Heating rate is 12 DEG C/min, after the sample of hydro-thermal process to be done is cooled to room temperature, is filtered sample using vacuum filtration pump
Obtained sample is placed in freezing and done by film forming to get LiFePO4/bacterial cellulose/graphene composite material film has been arrived
It is freeze-dried in dry machine；
(3) by the clean and dry scissors of the LiFePO4 of above-mentioned acquisition/bacterial cellulose/graphene composite material film
Thin rounded flakes are cut into, button cell internal diameter is dimensioned slightly smaller than.It is transferred into tube furnace later in argon gas stream and hydrogen
Carbonization treatment is carried out under air-flow protection, controlling the flow velocity of argon gas stream and hydrogen stream in entire carbonisation, (argon gas flow velocity is
180mL/min, hydrogen flow rate 20mL/min).The heating curve of tube furnace is set: by thin rounded flakes sample first with 5 DEG C/min
Heating rate be heated to 350 DEG C, 2 hours of heated at constant temperature, are hereafter heated to the heating rate of 8 DEG C/min at the temperature
650 DEG C, and heated at constant temperature 1.5 hours at the temperature, to guarantee that sample can be realized carbonization processing.It is last naturally cold
But target product is obtained to 20-25 degrees Celsius of room temperature: LiFePO4/bacterial cellulose/graphene composite material；
It (4) is button by the LiFePO4 Jing Guo carbonization treatment/bacterial cellulose/graphene composite material film sample assembly
Formula battery.Its specific assembly method are as follows: according to button cell structure chart in the glove box full of argon gas, successively by button electricity
Pond lower cover, spring leaf, lithium piece, diaphragm, the experiment pole piece (LiFePO4 of preparation/bacterial cellulose/graphene composite material film
Sample) it is assembled, while needing constantly to add electrolyte LB335C in this process, finally by button cell upper cover pressurization
Complete the assembling of button cell.(notes: the tools such as nonconductive tweezer must be used during assembled battery, to guarantee button electricity
Pond will not influence chemical property because operating short circuit).Use the electric battery test system of the indigo plant of model CT2001A and model
The electrochemical workstation of CHI602E carries out the test of chemical property to the above-mentioned button cell being completed.
Example 3
(1) firstly, Li3PO4 and citric acid are mixed in No. 1 beaker, dissolved, solution is ultrasonically treated,
Solution is in colorless and transparent sufficiently after reaction.Backward solution in be added graphene oxide suspension, to mixed solution carry out ultrasound
Processing is until mixed solution is ready to complete in No. 2 beakers.No. 2 beakers separately are taken, will be added by pretreated bacteria cellulose
Enter in the FeSO47H2O aqueous solution sufficiently dissolved, high-speed cutting decentralized processing carried out to it, need to equally control its revolving speed by
Lower starting speed gradually increases, and obtains bacteria cellulose/FeSO47H2O dispersion solution；LiFePO4, bacteria cellulose
Mass ratio with graphene is 5:2:2；
(2) hydro-thermal will be packed by the LiFePO4/bacteria cellulose/graphene composite dispersion liquid for sufficiently reacting and dispersing
In reaction kettle, set Muffle furnace heating curve: from 20-25 degrees Celsius of room temperature, heating temperature is 180 DEG C, soaking time 6h,
Heating rate is 10 DEG C/min, after the sample of hydro-thermal process to be done is cooled to room temperature, is filtered sample using vacuum filtration pump
Obtained sample is placed in freezing and done by film forming to get LiFePO4/bacterial cellulose/graphene composite material film has been arrived
It is freeze-dried in dry machine；
(3) by the clean and dry scissors of the LiFePO4 of above-mentioned acquisition/bacterial cellulose/graphene composite material film
Thin rounded flakes are cut into, button cell internal diameter is dimensioned slightly smaller than.It is transferred into tube furnace later in argon gas stream and hydrogen
Carbonization treatment is carried out under air-flow protection, controlling the flow velocity of argon gas stream and hydrogen stream in entire carbonisation, (argon gas flow velocity is
160mL/min, hydrogen flow rate 15mL/min).The heating curve of tube furnace is set: by thin rounded flakes sample first with 3 DEG C/min
Heating rate be heated to 320 DEG C, hereafter heated at constant temperature 2 hours at the temperature are heated to the heating rate of 6 DEG C/min
600 DEG C, and heated at constant temperature 2.5 hours at the temperature, to guarantee that sample can be realized carbonization processing.It is last naturally cold
But target product is obtained to 20-25 degrees Celsius of room temperature: LiFePO4/bacterial cellulose/graphene composite material；
It (4) is button by the LiFePO4 Jing Guo carbonization treatment/bacterial cellulose/graphene composite material film sample assembly
Formula battery.Its specific assembly method are as follows: according to button cell structure chart in the glove box full of argon gas, successively by button electricity
Pond lower cover, spring leaf, lithium piece, diaphragm, the experiment pole piece (LiFePO4 of preparation/bacterial cellulose/graphene composite material film
Sample) it is assembled, while needing constantly to add electrolyte LB335C in this process, finally by button cell upper cover pressurization
Complete the assembling of button cell.(notes: the tools such as nonconductive tweezer must be used during assembled battery, to guarantee button electricity
Pond will not influence chemical property because operating short circuit).Use the electric battery test system of the indigo plant of model CT2001A and model
The electrochemical workstation of CHI602E carries out the test of chemical property to the above-mentioned button cell being completed.
Example 4
(1) firstly, Li3PO4 and citric acid are mixed in No. 1 beaker, dissolved, solution is ultrasonically treated,
Solution is in colorless and transparent sufficiently after reaction.Backward solution in be added graphene oxide suspension, to mixed solution carry out ultrasound
Processing is until mixed solution is ready to complete in No. 2 beakers.No. 2 beakers separately are taken, will be added by pretreated bacteria cellulose
Enter in the FeSO47H2O aqueous solution sufficiently dissolved, high-speed cutting decentralized processing carried out to it, need to equally control its revolving speed by
Lower starting speed gradually increases, and obtains bacteria cellulose/FeSO47H2O dispersion solution；LiFePO4, bacteria cellulose
Mass ratio with graphene is 3:1:1；
(2) hydro-thermal will be packed by the LiFePO4/bacteria cellulose/graphene composite dispersion liquid for sufficiently reacting and dispersing
In reaction kettle, set Muffle furnace heating curve: from 20-25 degrees Celsius of room temperature, heating temperature is 150 DEG C, soaking time 8h,
Heating rate is 12 DEG C/min, after the sample of hydro-thermal process to be done is cooled to room temperature, is filtered sample using vacuum filtration pump
Obtained sample is placed in freezing and done by film forming to get LiFePO4/bacterial cellulose/graphene composite material film has been arrived
It is freeze-dried in dry machine；
(3) by the clean and dry scissors of the LiFePO4 of above-mentioned acquisition/bacterial cellulose/graphene composite material film
Thin rounded flakes are cut into, button cell internal diameter is dimensioned slightly smaller than.It is transferred into tube furnace later in argon gas stream and hydrogen
Carbonization treatment is carried out under air-flow protection, controlling the flow velocity of argon gas stream and hydrogen stream in entire carbonisation, (argon gas flow velocity is
150mL/min, hydrogen flow rate 20mL/min).The heating curve of tube furnace is set: by thin rounded flakes sample first with 4 DEG C/min
Heating rate be heated to 320 DEG C, hereafter heated at constant temperature 1.5 hours at the temperature are heated to the heating rate of 5 DEG C/min
620 DEG C, and heated at constant temperature 2.5 hours at the temperature, to guarantee that sample can be realized carbonization processing.It is last naturally cold
But target product is obtained to 20-25 degrees Celsius of room temperature: LiFePO4/bacterial cellulose/graphene composite material；
It (4) is button by the LiFePO4 Jing Guo carbonization treatment/bacterial cellulose/graphene composite material film sample assembly
Formula battery.Its specific assembly method are as follows: according to button cell structure chart in the glove box full of argon gas, successively by button electricity
Pond lower cover, spring leaf, lithium piece, diaphragm, the experiment pole piece (LiFePO4 of preparation/bacterial cellulose/graphene composite material film
Sample) it is assembled, while needing constantly to add electrolyte LB335C in this process, finally by button cell upper cover pressurization
Complete the assembling of button cell.(notes: the tools such as nonconductive tweezer must be used during assembled battery, to guarantee button electricity
Pond will not influence chemical property because operating short circuit).Use the electric battery test system of the indigo plant of model CT2001A and model
The electrochemical workstation of CHI602E carries out the test of chemical property to the above-mentioned button cell being completed.
Composite material embodiment 2-4 of the present invention can be achieved in the adjustment that content carries out preparation technology parameter according to the present invention
Preparation, and show the performance almost the same with embodiment 1.Illustrative description is done to the present invention above, it should illustrate
, in the case where not departing from core of the invention, any simple deformation, modification or other skilled in the art's energy
It is enough that the equivalent replacement of creative work is not spent to each fall within protection scope of the present invention.
Claims (10)
1. LiFePO4-bacteria cellulose-graphene composite material, which is characterized in that with lithium phosphate, citric acid and oxidation stone
The mixed solution of black alkene is added in the mixed solution of bacteria cellulose and ferrous sulfate, after hydro-thermal reaction and carbonization treatment
To LiFePO4-bacteria cellulose-graphene composite material, the mass ratio of LiFePO4, bacteria cellulose and graphene is
(1-5): (1-2): (1-2) carry out as steps described below:
Step 1, FeSO47H2O, Li3PO4 and citric acid are weighed by the mass ratio of the material 3:3:1, it, will using deionized water as solvent
Li3PO4 and citric acid are uniformly mixed and are added graphene oxide, and ultrasonic disperse is uniform, form the first solution；
In step 1, Li3PO4 and citric acid are mixed in beaker, dissolved, then solution is ultrasonically treated, sufficiently
Solution is in colorless and transparent after reaction, is ultrasonically treated to solution, and solution is in colorless and transparent sufficiently after reaction.
Step 2, bacteria cellulose has been added in the sufficiently aqueous solution of dissolution dispersion FeSO47H2O, high speed is carried out to it and is cut
Decentralized processing and ultrasonic disperse are cut, bacteria cellulose-FeSO47H2O is formed and disperses solution, i.e. the second solution；
Step 3, the first solution is added drop-wise in the second solution and forms finely dispersed LiFePO4-bacteria cellulose-graphite
Alkene composite dispersion liquid, and be fitted into hydrothermal reaction kettle, it heats up from 20-25 degrees Celsius of the room temperature heating rates with 8-12 DEG C/min
It to 150-200 DEG C and keeps the temperature 4-8h and is reacted, be filtered by vacuum after hydro-thermal reaction and sample is filtered into film forming to get to phosphoric acid
Iron lithium-bacteria cellulose-graphene composite material film is simultaneously freeze-dried；
Step 4, LiFePO4-bacteria cellulose-graphene composite material film step 3 obtained is transferred in tube furnace
Carbonizing reduction processing is carried out under argon gas stream and hydrogen stream protection, controls the stream of argon gas stream and hydrogen stream in entire carbonisation
Speed, argon gas flow velocity are 120-180mL/min, hydrogen flow rate 10-20mL/min, the heating curve setting of tube furnace are as follows: from room
Heating rate of 20-25 degrees Celsius of the temperature with 2-5 DEG C/min is heated to 300-350 DEG C, and heated at constant temperature 1-2 is small at the temperature
When, 600-650 DEG C hereafter are heated to the heating rate of 4-8 DEG C/min, and heated at constant temperature 1.5-2.5 hours at the temperature,
To guarantee that sample can be realized carbonization processing, 20-25 degrees Celsius of last cooled to room temperature obtains target product:
LiFePO4-bacteria cellulose-graphene composite material.
2. LiFePO4-bacteria cellulose-graphene composite material according to claim 1, which is characterized in that phosphoric acid
The mass ratio of iron lithium, bacteria cellulose and graphene is (3-5): (1-2): (1-2), bacteria cellulose and graphene are preferred
For equal mass ratioes.
3. LiFePO4-bacteria cellulose-graphene composite material according to claim 1, which is characterized in that in step
In rapid 3,180-200 DEG C is warming up to from 20-25 degrees Celsius of the room temperature heating rates with 8-12 DEG C/min and keeps the temperature 6-8h progress instead
It answers.
4. LiFePO4-bacteria cellulose-graphene composite material according to claim 1, which is characterized in that in step
In rapid 3, using being at the uniform velocity added dropwise, rate of addition is 5-10ml per minute.
5. LiFePO4-bacteria cellulose-graphene composite material according to claim 1, which is characterized in that in step
In rapid 4, the flow velocity of argon gas stream and hydrogen stream in entire carbonisation is controlled, argon gas flow velocity is 120-160mL/min, hydrogen flow rate
Heating curve for 15-20mL/min, tube furnace is set are as follows: from 20-25 degrees Celsius of the room temperature heating rates with 2-5 DEG C/min
320-350 DEG C are heated to, hereafter the heated at constant temperature 1-1.5 hours at the temperature is heated to the heating rate of 4-8 DEG C/min
620-650 DEG C, and heated at constant temperature 2-2.5 hours at the temperature, to guarantee that sample can be realized carbonization processing, most
20-25 degrees Celsius of cooled to room temperature afterwards.
6. LiFePO4-bacteria cellulose-graphene composite material preparation method, which is characterized in that LiFePO4, bacterium
The mass ratio of cellulose and graphene is (1-5): (1-2): (1-2), is carried out as steps described below:
Step 1, FeSO47H2O, Li3PO4 and citric acid are weighed by the mass ratio of the material 3:3:1, it, will using deionized water as solvent
Li3PO4 and citric acid are uniformly mixed and are added graphene oxide, and ultrasonic disperse is uniform, form the first solution；
In step 1, Li3PO4 and citric acid are mixed in beaker, dissolved, then solution is ultrasonically treated, sufficiently
Solution is in colorless and transparent after reaction, is ultrasonically treated to solution, and solution is in colorless and transparent sufficiently after reaction.
Step 2, bacteria cellulose has been added in the sufficiently aqueous solution of dissolution dispersion FeSO47H2O, high speed is carried out to it and is cut
Decentralized processing and ultrasonic disperse are cut, bacteria cellulose-FeSO47H2O is formed and disperses solution, i.e. the second solution；
Step 3, the first solution is added drop-wise in the second solution and forms finely dispersed LiFePO4-bacteria cellulose-graphite
Alkene composite dispersion liquid, and be fitted into hydrothermal reaction kettle, it heats up from 20-25 degrees Celsius of the room temperature heating rates with 8-12 DEG C/min
It to 150-200 DEG C and keeps the temperature 4-8h and is reacted, be filtered by vacuum after hydro-thermal reaction and sample is filtered into film forming to get to phosphoric acid
Iron lithium-bacteria cellulose-graphene composite material film is simultaneously freeze-dried；
Step 4, LiFePO4-bacteria cellulose-graphene composite material film step 3 obtained is transferred in tube furnace
Carbonizing reduction processing is carried out under argon gas stream and hydrogen stream protection, controls the stream of argon gas stream and hydrogen stream in entire carbonisation
Speed, argon gas flow velocity are 120-180mL/min, hydrogen flow rate 10-20mL/min, the heating curve setting of tube furnace are as follows: from room
Heating rate of 20-25 degrees Celsius of the temperature with 2-5 DEG C/min is heated to 300-350 DEG C, and heated at constant temperature 1-2 is small at the temperature
When, 600-650 DEG C hereafter are heated to the heating rate of 4-8 DEG C/min, and heated at constant temperature 1.5-2.5 hours at the temperature,
To guarantee that sample can be realized carbonization processing, 20-25 degrees Celsius of last cooled to room temperature obtains target product:
LiFePO4-bacteria cellulose-graphene composite material.
7. LiFePO4 according to claim 6-bacteria cellulose-graphene composite material preparation method, special
Sign is, the mass ratio of LiFePO4, bacteria cellulose and graphene is (3-5): (1-2): (1-2), bacteria cellulose and
Graphene preferably waits mass ratioes.
8. LiFePO4 according to claim 6-bacteria cellulose-graphene composite material preparation method, special
Sign is, in step 3, is warming up to 180-200 DEG C from 20-25 degrees Celsius of the room temperature heating rates with 8-12 DEG C/min and protects
Warm 6-8h is reacted；Using being at the uniform velocity added dropwise, rate of addition is 5-10ml per minute.
9. LiFePO4 according to claim 6-bacteria cellulose-graphene composite material preparation method, special
Sign is, in step 4, controls the flow velocity of argon gas stream and hydrogen stream in entire carbonisation, argon gas flow velocity is 120-160mL/
Min, hydrogen flow rate 15-20mL/min, the heating curve setting of tube furnace are as follows: from 20-25 degrees Celsius of room temperature with 2-5 DEG C/
The heating rate of min is heated to 320-350 DEG C, the heated at constant temperature 1-1.5 hours at the temperature, hereafter with 4-8 DEG C/min's
Heating rate is heated to 620-650 DEG C, and heated at constant temperature 2-2.5 hours at the temperature, to guarantee that sample can be realized
Full carbonization treatment, 20-25 degrees Celsius of last cooled to room temperature.
10. LiFePO4-bacteria cellulose-graphene composite material as described in claim 1 is preparing anode material
Application in material.
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