CN109256528B - Lithium iron phosphate-bacterial cellulose-graphene composite material and preparation method and application thereof - Google Patents
Lithium iron phosphate-bacterial cellulose-graphene composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a lithium iron phosphate-bacterial cellulose-graphene composite material and a preparation method and application thereof. The material is applied to the anode material of the lithium ion battery. The material shows excellent cycle performance and higher charge-discharge capacity, and has excellent flexibility and self-supporting property.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a flexible, tough and high-discharge-capacity lithium ion battery anode material prepared by using lithium iron phosphate, bacterial cellulose and graphene as raw materials, so that anode support is provided for preparing an integrated flexible battery, and a prepared target electrode can be widely applied to fabrics and under the condition of variable mechanical environments and has potential application prospects in many fields such as aerospace and the like.
Background
With the attention of people to the environmental and energy problems, more and more attention is focused on new natural energy sources such as wind energy, solar energy, tidal energy and the like which have the advantages of high efficiency, renewability, environmental friendliness and the like. However, it is not easy to find that the above natural energy cannot realize continuous action, and if the natural energy is to be utilized in large-scale commercialization to become a core pillar in a new energy structure, an energy storage device capable of matching with the characteristics of the natural energy is required. The battery is a device capable of directly converting chemical energy into electric energy, and is undoubtedly an energy storage device with the most research and utilization values in the current society due to the high energy utilization rate and the simple working principle. Meanwhile, the rapid development of the electronic information technology neighborhood and related disciplines greatly promotes the development process of miniaturization of electronic instruments and equipment, and in order to meet the increasingly severe general requirements, the market gradually puts higher requirements on the performance quality and the cost budget of the power supply. In addition, with the increasing environmental and energy pressure facing the world, after the electric vehicle is continuously innovated, researched and developed, and updated, the electric vehicle gradually replaces the traditional vehicle so as to thoroughly solve a series of problems caused by fossil energy consumption, and becomes a necessary trend of the development of the times, wherein a battery system for providing power is a core link of the development process of the left and right electric vehicles, and based on the research background, it is urgent to research and develop a high-specific-energy battery with low cost, environmental friendliness and excellent comprehensive performance as soon as possible.
Goodenough et al considered the use of lithium iron phosphate (LiFePO4) as the lithium ion battery anode material for the first time in 1997, and once it was proposed, they had drawn much attention because of its excellent properties such as abundant raw material sources, long cycle life, flat charging/discharging platform (3.4V vs. Li +/Li), and high theoretical capacity (170m Ah. g-1). Lithium iron phosphate plays an important role in the field of batteries as a positive electrode material with great development prospects. Bacterial cellulose, as a natural polymer, has received extensive attention due to its unique physicochemical properties, and the exploration of its properties and applications has achieved certain results at present. Graphene is a two-dimensional carbon nanomaterial with a single atomic thickness, has excellent electrical, optical, thermal and mechanical properties, and a larger specific surface area than other carbon-based materials (including carbon nanotubes, carbon fibers, graphite, etc.), and thus is an ideal material for preparing various high-strength structural materials, catalysts and energy devices.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a lithium iron phosphate-bacterial cellulose-graphene composite material and a preparation method and application thereof.
The technical purpose of the invention is realized by the following technical scheme:
the lithium iron phosphate-bacterial cellulose-graphene composite material is prepared by adding a mixed solution of lithium phosphate, citric acid and graphene oxide into a mixed solution of bacterial cellulose and ferrous sulfate, and performing hydrothermal reaction and carbonization treatment, wherein the mass ratio of the lithium iron phosphate to the bacterial cellulose to the graphene is (1-5): (1-2): (1-2) according to the following steps:
in the step 1, Li3PO4 and citric acid are mixed, stirred and dissolved in a beaker, the solution is subjected to ultrasonic treatment, the solution is colorless and transparent after full reaction, and the solution is subjected to ultrasonic treatment, and the solution is colorless and transparent after full reaction.
and 4, transferring the lithium iron phosphate-bacterial cellulose-graphene composite material film obtained in the step 3 into a tubular furnace to perform carbonization reduction treatment under the protection of argon flow and hydrogen flow, controlling the flow rates of the argon flow and the hydrogen flow in the whole carbonization process, wherein the argon flow rate is 180mL/min, the hydrogen flow rate is 10-20mL/min, and the temperature rise curve of the tubular furnace is set as follows: heating the sample to 300-350 ℃ from the room temperature of 20-25 ℃ at the heating rate of 2-5 ℃/min, heating the sample at the temperature for 1-2 hours at the constant temperature, heating the sample to 600-650 ℃ at the heating rate of 4-8 ℃/min, heating the sample at the temperature for 1.5-2.5 hours at the constant temperature, thus ensuring that the sample can be completely carbonized, and finally naturally cooling the sample to the room temperature of 20-25 ℃ to obtain a target product: lithium iron phosphate-bacterial cellulose-graphene composite material.
In the technical scheme of the invention, the mass ratio of the lithium iron phosphate to the bacterial cellulose to the graphene is (3-5): (1-2): (1-2), the bacterial cellulose and the graphene are preferably in an equal mass ratio.
In step 3, the temperature is raised from room temperature of 20-25 ℃ to 180-200 ℃ at the temperature raising rate of 8-12 ℃/min and the temperature is kept for 6-8h for reaction.
In the step 3, the uniform dripping is adopted, and the dripping speed is 5-10 ml per minute.
In step 4, the flow rates of argon flow and hydrogen flow in the whole carbonization process are controlled, the flow rate of argon flow is 160mL/min and the flow rate of hydrogen is 15-20mL/min, and the temperature rise curve of the tubular furnace is set as follows: heating the sample to 320-350 ℃ from 20-25 ℃ at the heating rate of 2-5 ℃/min, heating the sample at the temperature for 1-1.5 hours at the constant temperature, heating the sample to 620-650 ℃ at the heating rate of 4-8 ℃/min, heating the sample at the temperature for 2-2.5 hours at the constant temperature, and finally naturally cooling the sample to 20-25 ℃.
The lithium iron phosphate/bacterial cellulose/graphene composite material is successfully prepared and applied as the lithium ion battery anode material. The material shows excellent cycle performance and higher charge-discharge capacity, and has excellent flexibility and self-supporting property.
Drawings
Fig. 1 is a schematic flow chart of a preparation process of the lithium iron phosphate/bacterial cellulose/graphene composite material.
Fig. 2 is a scanning electron microscope photograph of a sample of the lithium iron phosphate/bacterial cellulose/graphene composite material of the present invention.
Fig. 3 is a transmission electron microscope photograph of a sample of the lithium iron phosphate/bacterial cellulose/graphene composite material of the present invention.
Fig. 4 is a CV curve test of a lithium iron phosphate/bacterial cellulose/graphene composite material sample after high-temperature carbonization at 600 ℃ in the invention.
Fig. 5 is a charge-discharge curve of a sample of the lithium iron phosphate/bacterial cellulose/graphene composite material carbonized at a high temperature of 600 ℃ in the present invention.
Fig. 6 is a cycle performance diagram of a lithium iron phosphate/bacterial cellulose/graphene composite material sample after high-temperature carbonization at 600 ℃ in the invention.
Detailed Description
The technical solution of the present invention is explained below by specific examples.
Bacterial Cellulose (BC) is a generic term for cellulose synthesized by any microorganism of the genera Acetobacter (Acetobacter), Agrobacterium (Agrobacterium), Rhizobium (Rhizobium), Sarcina (Sarcina), and the like under different conditions; bacterial cellulose (a class of high molecular compounds generated by gluconacetobacter xylinus, fibers generated by fermentation of natural strains in nature and the smallest natural fibers in nature, the fiber diameter of the fibers is about 20-100 nm, and the size of a reticular pore structure of the fibers is about 0.5-1.0 um) purchased from Hainan Guangyu Biotechnology Limited is pretreated, and is subjected to high-speed mechanical cutting and dispersion in deionized water, then the filtration is carried out, a sample is repeatedly washed until the pH value is stabilized at neutral, and the sample is dried and stored for later use.
The method for preparing the graphene oxide by taking graphite as a raw material comprises the following specific steps:
(1) and (3) low-temperature reaction stage of graphene oxide: weighing 20mL of concentrated sulfuric acid, pouring into a beaker, placing the beaker into an ice bath to cool to below 3 ℃, weighing 0.5g of graphite powder and 0.2g of sodium nitrate, placing into the beaker, slowly adding 2.5g of potassium permanganate after 1h, controlling the temperature to be not more than 8 ℃, and reacting for 1.5 h.
(2) And (3) intermediate-temperature reaction stage of graphene oxide: and (3) transferring the beaker to a constant-temperature water bath kettle, controlling the temperature of the water bath to be 35-40 ℃, reacting for 0.5h, and keeping stirring for 100-150 r/min.
(3) High-temperature reaction stage of graphene oxide: 70mL of deionized water is slowly added into the obtained mixed solution, the temperature of the mixed solution is controlled to be 90 ℃, and the reaction is carried out for 0.5h, during which the mixed solution is kept moderately stirred for 100-150 r/min.
(4) After the high-temperature reaction, 50mL of deionized water is added to stop the reaction, 10mL of hydrogen peroxide (30 vol% aqueous hydrogen peroxide) is added to react for 10min, and then 30mL of hydrochloric acid (10 vol% aqueous hydrogen chloride) is added. And (3) carrying out low-speed centrifugal washing to remove excessive acid and byproducts, dispersing the washed neutral graphite oxide in water, stripping the sample by using ultrasonic waves for 30-60 min, centrifuging at a rotating speed of 2000 r.min < -1 > for 20min after the sample is finished, taking the supernatant as a graphene oxide suspension, and taking out the sample for storage.
According to the mass ratio of 3:3:1, FeSO4 & 7H2O, Li3PO4 and citric acid are weighed, deionized water is used as a solvent, and a solution is prepared. When feeding, feeding is carried out according to the feeding ratio of the lithium iron phosphate, the bacterial cellulose and the graphene, namely the mass ratio of the lithium iron phosphate to the bacterial cellulose to the graphene is (1-5): (1-2): (1-2), preferably, the bacterial cellulose and the graphene are in an equal mass ratio; selecting the prepared graphene oxide turbid liquid for feeding according to the amount of graphene and the concentration of the graphene oxide turbid liquid; selecting a feeding material of the bacterial cellulose during preparation according to the using amount of the bacterial cellulose; according to the using amount of the lithium iron phosphate, the using amounts of FeSO4 & 7H2O, Li3PO4 and citric acid during preparation are selected, and the ratio of the three substances is 3:3: 1.
example 1
(1) First, Li3PO4 and citric acid were mixed, stirred, and dissolved in a No. 1 beaker, and the solution was sonicated, and after a sufficient reaction, the solution was colorless and transparent. And adding the graphene oxide turbid liquid into the solution, and carrying out ultrasonic treatment on the mixed solution until the mixed solution in the No. 2 beaker is prepared. Adding the pretreated bacterial cellulose into the fully dissolved FeSO4 & 7H2O aqueous solution in another No. 2 beaker, and carrying out high-speed cutting and dispersing treatment on the bacterial cellulose, wherein the rotating speed of the beaker is also controlled to be gradually increased from a lower starting speed, so as to obtain a bacterial cellulose/FeSO 4 & 7H2O dispersed solution; the mass ratio of the lithium iron phosphate to the bacterial cellulose to the graphene is 1: 1: 1;
(2) filling the fully reacted and dispersed lithium iron phosphate/bacterial cellulose/graphene composite dispersion liquid into a hydrothermal reaction kettle, and setting a muffle furnace temperature rise curve: after the sample subjected to the hydrothermal treatment is cooled to room temperature from 20-25 ℃, the heating temperature is 150 ℃, the heat preservation time is 4 hours, the heating rate is 8 ℃/min, the sample is subjected to suction filtration and film forming by using a vacuum suction filtration pump, so that a lithium iron phosphate/bacterial cellulose/graphene composite material film is obtained, and the prepared sample is placed in a freeze dryer for freeze drying;
(3) and shearing the obtained lithium iron phosphate/bacterial cellulose/graphene composite material film into a round sheet with a clean and dry scissors, wherein the size of the round sheet is slightly smaller than the inner diameter of the button cell. Then the obtained product is transferred into a tube furnace to be carbonized under the protection of argon flow and hydrogen flow, and the flow rates of the argon flow and the hydrogen flow in the whole carbonization process are controlled (the flow rate of the argon flow is 120mL/min, and the flow rate of the hydrogen is 10 mL/min). Setting a temperature rise curve of the tube furnace: heating a circular thin sheet sample to 300 ℃ at a heating rate of 2 ℃/min, heating the sample at the constant temperature for 1 hour, heating the sample to 600 ℃ at a heating rate of 4 ℃/min, and heating the sample at the constant temperature for 1.5 hours, thereby ensuring that the sample can be completely carbonized. And finally, naturally cooling to room temperature of 20-25 ℃ to obtain a target product: lithium iron phosphate/bacterial cellulose/graphene composite material;
(4) assembling the carbonized lithium iron phosphate/bacterial cellulose/graphene composite material film sample into a button cell. The specific assembling method comprises the following steps: and sequentially assembling a button cell lower cover, a spring piece, a lithium piece, a diaphragm and an experimental pole piece (a prepared lithium iron phosphate/bacterial cellulose/graphene composite material film sample is used as a battery anode material) in a glove box filled with argon according to a button cell structure diagram, meanwhile, continuously adding an electrolyte LB335C in the process, and finally, pressurizing and sealing the button cell upper cover to complete the assembly of the button cell. (Note: during the assembly of the cell, insulation tweezers and other tools are necessary to ensure that the electrochemical performance of the button cell is not affected by short circuit during operation). The assembled button cells were tested for electrochemical performance using a blue cell testing system model CT2001A and an electrochemical workstation model CHI 602E.
The preparation process of the lithium iron phosphate/bacterial cellulose/graphene composite material in example 1 is shown in fig. 1.
In a scanning electron microscope photograph (as shown in fig. 2) of a sample of the lithium iron phosphate/bacterial cellulose/graphene composite material in example 1, it can be observed from (a) that the lithium iron phosphate/bacterial cellulose/graphene composite material prepared through experiments is of a large-sheet-layer structure and is uniformly spread in a visual field, and a sheet-layer framework of the lithium iron phosphate/bacterial cellulose/graphene composite material is constructed by graphene oxide sheets with a huge specific surface area. The structural characteristics of the lithium iron phosphate/bacterial cellulose/graphene composite material in the dot-line-surface mode can be clearly seen in the step (b): lithium iron phosphate particles are uniformly distributed on the graphene sheet layer, and meanwhile, the sheet layer is connected with the sheet layer through fibers, so that the special three-dimensional multi-sheet-layer interconnection structure is finally formed. Fibers attached to the graphene sheet layer and small-range agglomerated lithium iron phosphate particles can be seen in the step (c), which shows that three core raw material monomers (lithium iron phosphate particles, the graphene sheet layer and the chopped fibers) can be effectively compounded with each other and are mutually connected to further enhance the structural stability of the composite material, improve the electronic conductivity and the ion diffusion rate of the composite material and enhance the comprehensive performance of the battery.
In the transmission electron microscope photograph (as shown in fig. 3) of the sample of the lithium iron phosphate/bacterial cellulose/graphene composite material in example 1, it can be seen that the fiber part of the network structure of the sample is gradually loosened after the sample is carbonized at 600 ℃, and the fiber diameter is reduced.
The CV curve test (shown in fig. 4) of the 600 ℃ high-temperature carbonized lithium iron phosphate/bacterial cellulose/graphene composite material sample in example 1 reflects the CV scanning curves of the experimentally prepared composite material in the first two cycles, wherein the scanning speed of the CV curve in the graph is 0.5mv. s-1
The charge-discharge curve (shown in fig. 5) of the 600 ℃ high-temperature carbonized lithium iron phosphate/bacterial cellulose/graphene composite material sample in example 1 shows the first three constant current discharge curves and cycle performance of the 600 ℃ carbonized composite material sample within the interval of 2-4.5V and at the current density of 20 mA/g. It can be clearly seen from the figure that, in the first discharging process of the lithium iron phosphate/bacterial cellulose/graphene composite material, an obvious discharging platform appears at about 3.5V, and in the second and third following cycles, the discharging platforms are stably superposed. In addition, the capacity of the lithium iron phosphate/bacterial cellulose/graphene composite material which is prepared through experiments and discharges for the first time under the current density of 20mA/g is 122 mAh/g. When the cycle continues, the second and third charge-discharge curves almost completely coincide, which fully indicates that the battery capacity of the button cell assembled by the experiment tends to be stable after continuous cycle.
The cycle performance of the 600 ℃ high-temperature carbonized lithium iron phosphate/bacterial cellulose/graphene composite material sample in example 1 (as shown in fig. 6) is that after 40 cycles, the reversible capacity of the 600 ℃ carbonized composite material sample is still maintained above 120 mAh/g. Meanwhile, the coulombic efficiency close to 1 can be still kept after 40 groups of cycles of the composite material sample, and the anode prepared from the composite material is proved to have excellent cycle performance.
Example 2
(1) First, Li3PO4 and citric acid were mixed, stirred, and dissolved in a No. 1 beaker, and the solution was sonicated, and after a sufficient reaction, the solution was colorless and transparent. And adding the graphene oxide turbid liquid into the solution, and carrying out ultrasonic treatment on the mixed solution until the mixed solution in the No. 2 beaker is prepared. Adding the pretreated bacterial cellulose into the fully dissolved FeSO4 & 7H2O aqueous solution in another No. 2 beaker, and carrying out high-speed cutting and dispersing treatment on the bacterial cellulose, wherein the rotating speed of the beaker is also controlled to be gradually increased from a lower starting speed, so as to obtain a bacterial cellulose/FeSO 4 & 7H2O dispersed solution; the mass ratio of the lithium iron phosphate to the bacterial cellulose to the graphene is 5: 1: 1;
(2) filling the fully reacted and dispersed lithium iron phosphate/bacterial cellulose/graphene composite dispersion liquid into a hydrothermal reaction kettle, and setting a muffle furnace temperature rise curve: after a sample subjected to hydrothermal treatment is cooled to room temperature from 20-25 ℃, the heating temperature is 150 ℃, the heat preservation time is 8 hours, the heating rate is 12 ℃/min, the sample is subjected to suction filtration and film forming by using a vacuum suction filtration pump, so that a lithium iron phosphate/bacterial cellulose/graphene composite material film is obtained, and the prepared sample is placed in a freeze dryer for freeze drying;
(3) and shearing the obtained lithium iron phosphate/bacterial cellulose/graphene composite material film into a round sheet with a clean and dry scissors, wherein the size of the round sheet is slightly smaller than the inner diameter of the button cell. Then the obtained product is transferred into a tube furnace to be carbonized under the protection of argon flow and hydrogen flow, and the flow rates of the argon flow and the hydrogen flow in the whole carbonization process are controlled (the flow rate of the argon flow is 180mL/min, and the flow rate of the hydrogen is 20 mL/min). Setting a temperature rise curve of the tube furnace: heating a circular thin sheet sample to 350 ℃ at a heating rate of 5 ℃/min, heating the sample at the constant temperature for 2 hours, then heating the sample to 650 ℃ at a heating rate of 8 ℃/min, and heating the sample at the constant temperature for 1.5 hours, thereby ensuring that the sample can be completely carbonized. And finally, naturally cooling to room temperature of 20-25 ℃ to obtain a target product: lithium iron phosphate/bacterial cellulose/graphene composite material;
(4) assembling the carbonized lithium iron phosphate/bacterial cellulose/graphene composite material film sample into a button cell. The specific assembling method comprises the following steps: and (3) assembling a lower cover of the button cell, a spring piece, a lithium piece, a diaphragm and an experimental pole piece (a prepared lithium iron phosphate/bacterial cellulose/graphene composite material film sample) in turn in a glove box filled with argon according to a structure diagram of the button cell, continuously adding an electrolyte LB335C in the process, and finally, pressurizing and sealing an upper cover of the button cell to complete the assembly of the button cell. (Note: during the assembly of the cell, insulation tweezers and other tools are necessary to ensure that the electrochemical performance of the button cell is not affected by short circuit during operation). The assembled button cells were tested for electrochemical performance using a blue cell testing system model CT2001A and an electrochemical workstation model CHI 602E.
Example 3
(1) First, Li3PO4 and citric acid were mixed, stirred, and dissolved in a No. 1 beaker, and the solution was sonicated, and after a sufficient reaction, the solution was colorless and transparent. And adding the graphene oxide turbid liquid into the solution, and carrying out ultrasonic treatment on the mixed solution until the mixed solution in the No. 2 beaker is prepared. Adding the pretreated bacterial cellulose into the fully dissolved FeSO4 & 7H2O aqueous solution in another No. 2 beaker, and carrying out high-speed cutting and dispersing treatment on the bacterial cellulose, wherein the rotating speed of the beaker is also controlled to be gradually increased from a lower starting speed, so as to obtain a bacterial cellulose/FeSO 4 & 7H2O dispersed solution; the mass ratio of the lithium iron phosphate to the bacterial cellulose to the graphene is 5: 2: 2;
(2) filling the fully reacted and dispersed lithium iron phosphate/bacterial cellulose/graphene composite dispersion liquid into a hydrothermal reaction kettle, and setting a muffle furnace temperature rise curve: after a sample subjected to hydrothermal treatment is cooled to room temperature from 20-25 ℃, the heating temperature is 180 ℃, the heat preservation time is 6 hours, the heating rate is 10 ℃/min, the sample is subjected to suction filtration and film forming by using a vacuum suction filtration pump, so that a lithium iron phosphate/bacterial cellulose/graphene composite material film is obtained, and the prepared sample is placed in a freeze dryer for freeze drying;
(3) and shearing the obtained lithium iron phosphate/bacterial cellulose/graphene composite material film into a round sheet with a clean and dry scissors, wherein the size of the round sheet is slightly smaller than the inner diameter of the button cell. Then the obtained product is transferred into a tube furnace to be carbonized under the protection of argon flow and hydrogen flow, and the flow rates of the argon flow and the hydrogen flow in the whole carbonization process are controlled (the flow rate of the argon flow is 160mL/min, and the flow rate of the hydrogen is 15 mL/min). Setting a temperature rise curve of the tube furnace: heating a circular slice sample to 320 ℃ at a heating rate of 3 ℃/min, heating the sample at the constant temperature for 2 hours, then heating the sample to 600 ℃ at a heating rate of 6 ℃/min, and heating the sample at the constant temperature for 2.5 hours, thereby ensuring that the sample can be completely carbonized. And finally, naturally cooling to room temperature of 20-25 ℃ to obtain a target product: lithium iron phosphate/bacterial cellulose/graphene composite material;
(4) assembling the carbonized lithium iron phosphate/bacterial cellulose/graphene composite material film sample into a button cell. The specific assembling method comprises the following steps: and (3) assembling a lower cover of the button cell, a spring piece, a lithium piece, a diaphragm and an experimental pole piece (a prepared lithium iron phosphate/bacterial cellulose/graphene composite material film sample) in turn in a glove box filled with argon according to a structure diagram of the button cell, continuously adding an electrolyte LB335C in the process, and finally, pressurizing and sealing an upper cover of the button cell to complete the assembly of the button cell. (Note: during the assembly of the cell, insulation tweezers and other tools are necessary to ensure that the electrochemical performance of the button cell is not affected by short circuit during operation). The assembled button cells were tested for electrochemical performance using a blue cell testing system model CT2001A and an electrochemical workstation model CHI 602E.
Example 4
(1) First, Li3PO4 and citric acid were mixed, stirred, and dissolved in a No. 1 beaker, and the solution was sonicated, and after a sufficient reaction, the solution was colorless and transparent. And adding the graphene oxide turbid liquid into the solution, and carrying out ultrasonic treatment on the mixed solution until the mixed solution in the No. 2 beaker is prepared. Adding the pretreated bacterial cellulose into the fully dissolved FeSO4 & 7H2O aqueous solution in another No. 2 beaker, and carrying out high-speed cutting and dispersing treatment on the bacterial cellulose, wherein the rotating speed of the beaker is also controlled to be gradually increased from a lower starting speed, so as to obtain a bacterial cellulose/FeSO 4 & 7H2O dispersed solution; the mass ratio of the lithium iron phosphate to the bacterial cellulose to the graphene is 3: 1: 1;
(2) filling the fully reacted and dispersed lithium iron phosphate/bacterial cellulose/graphene composite dispersion liquid into a hydrothermal reaction kettle, and setting a muffle furnace temperature rise curve: after a sample subjected to hydrothermal treatment is cooled to room temperature from 20-25 ℃, the heating temperature is 150 ℃, the heat preservation time is 8 hours, the heating rate is 12 ℃/min, the sample is subjected to suction filtration and film forming by using a vacuum suction filtration pump, so that a lithium iron phosphate/bacterial cellulose/graphene composite material film is obtained, and the prepared sample is placed in a freeze dryer for freeze drying;
(3) and shearing the obtained lithium iron phosphate/bacterial cellulose/graphene composite material film into a round sheet with a clean and dry scissors, wherein the size of the round sheet is slightly smaller than the inner diameter of the button cell. Then the obtained product is transferred into a tube furnace to be carbonized under the protection of argon flow and hydrogen flow, and the flow rates of the argon flow and the hydrogen flow in the whole carbonization process are controlled (the flow rate of the argon flow is 150mL/min, and the flow rate of the hydrogen is 20 mL/min). Setting a temperature rise curve of the tube furnace: heating a circular thin slice sample to 320 ℃ at a heating rate of 4 ℃/min, heating the sample at the constant temperature for 1.5 hours, then heating the sample to 620 ℃ at a heating rate of 5 ℃/min, and heating the sample at the constant temperature for 2.5 hours, thereby ensuring that the sample can be completely carbonized. And finally, naturally cooling to room temperature of 20-25 ℃ to obtain a target product: lithium iron phosphate/bacterial cellulose/graphene composite material;
(4) assembling the carbonized lithium iron phosphate/bacterial cellulose/graphene composite material film sample into a button cell. The specific assembling method comprises the following steps: and (3) assembling a lower cover of the button cell, a spring piece, a lithium piece, a diaphragm and an experimental pole piece (a prepared lithium iron phosphate/bacterial cellulose/graphene composite material film sample) in turn in a glove box filled with argon according to a structure diagram of the button cell, continuously adding an electrolyte LB335C in the process, and finally, pressurizing and sealing an upper cover of the button cell to complete the assembly of the button cell. (Note: during the assembly of the cell, insulation tweezers and other tools are necessary to ensure that the electrochemical performance of the button cell is not affected by short circuit during operation). The assembled button cells were tested for electrochemical performance using a blue cell testing system model CT2001A and an electrochemical workstation model CHI 602E.
The composite materials of examples 2-4 of the present invention were prepared according to the present disclosure by adjusting the process parameters and exhibited substantially the same properties as example 1. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (12)
1. The lithium iron phosphate-bacterial cellulose-graphene composite material is characterized in that a mixed solution of lithium phosphate, citric acid and graphene oxide is added into a mixed solution of bacterial cellulose and ferrous sulfate, and the mixed solution is subjected to hydrothermal reaction and carbonization treatment to obtain the lithium iron phosphate-bacterial cellulose-graphene composite material, wherein the mass ratio of the lithium iron phosphate to the bacterial cellulose to the graphene is (1-5): (1-2): (1-2) according to the following steps:
step 1, weighing FeSO 4.7H 2O, Li3PO4 and citric acid according to the mass ratio of 3:3:1, taking deionized water as a solvent, uniformly mixing Li3PO4 and citric acid, adding graphene oxide, and performing ultrasonic dispersion uniformly to form a first solution;
in the step 1, mixing, stirring and dissolving Li3PO4 and citric acid in a beaker, then carrying out ultrasonic treatment on the solution, wherein the solution is colorless and transparent after full reaction, and the solution is colorless and transparent after full reaction;
step 2, adding the bacterial cellulose into an aqueous solution which is fully dissolved and dispersed with FeSO4 & 7H2O, carrying out high-speed cutting dispersion treatment and ultrasonic dispersion on the bacterial cellulose to form a bacterial cellulose-FeSO 4 & 7H2O dispersion solution, namely a second solution;
step 3, dropwise adding the first solution into the second solution to form uniformly dispersed lithium iron phosphate-bacterial cellulose-graphene composite dispersion liquid, putting the uniformly dispersed lithium iron phosphate-bacterial cellulose-graphene composite dispersion liquid into a hydrothermal reaction kettle, heating the mixture to 150-200 ℃ from the room temperature of 20-25 ℃ at the heating rate of 8-12 ℃/min, preserving heat for 4-8 hours for reaction, carrying out vacuum filtration after hydrothermal reaction to filter and filter a sample into a film, and obtaining a lithium iron phosphate-bacterial cellulose-graphene composite material film, and freeze-drying the film;
and 4, transferring the lithium iron phosphate-bacterial cellulose-graphene composite material film obtained in the step 3 into a tubular furnace to perform carbonization reduction treatment under the protection of argon flow and hydrogen flow, controlling the flow rates of the argon flow and the hydrogen flow in the whole carbonization process, wherein the argon flow rate is 180mL/min, the hydrogen flow rate is 10-20mL/min, and the temperature rise curve of the tubular furnace is set as follows: heating the sample to 300-350 ℃ from the room temperature of 20-25 ℃ at the heating rate of 2-5 ℃/min, heating the sample at the temperature for 1-2 hours at the constant temperature, heating the sample to 600-650 ℃ at the heating rate of 4-8 ℃/min, heating the sample at the temperature for 1.5-2.5 hours at the constant temperature, thus ensuring that the sample can be completely carbonized, and finally naturally cooling the sample to the room temperature of 20-25 ℃ to obtain a target product: lithium iron phosphate-bacterial cellulose-graphene composite material.
2. The lithium iron phosphate-bacterial cellulose-graphene composite material according to claim 1, wherein the mass ratio of the lithium iron phosphate to the bacterial cellulose to the graphene is (3-5): (1-2): (1-2).
3. The lithium iron phosphate-bacterial cellulose-graphene composite material according to claim 2, wherein the bacterial cellulose and the graphene are in an equal mass ratio.
4. The lithium iron phosphate-bacterial cellulose-graphene composite material as claimed in claim 1, wherein in step 3, the temperature is raised from room temperature 20-25 ℃ to 180-200 ℃ at a temperature raising rate of 8-12 ℃/min and the temperature is maintained for 6-8h for reaction.
5. The lithium iron phosphate-bacterial cellulose-graphene composite material according to claim 1, wherein in step 3, uniform dropping is performed at a dropping speed of 5-10 ml per minute.
6. The lithium iron phosphate-bacterial cellulose-graphene composite material of claim 1, wherein in step 4, the flow rates of argon flow and hydrogen flow in the whole carbonization process are controlled, the flow rate of argon flow is 160mL/min and the flow rate of hydrogen is 15-20mL/min, and the temperature rise curve of the tube furnace is set as follows: heating the sample to 320-350 ℃ from 20-25 ℃ at the heating rate of 2-5 ℃/min, heating the sample at the temperature for 1-1.5 hours at the constant temperature, heating the sample to 620-650 ℃ at the heating rate of 4-8 ℃/min, heating the sample at the temperature for 2-2.5 hours at the constant temperature, and finally naturally cooling the sample to 20-25 ℃.
7. The preparation method of the lithium iron phosphate-bacterial cellulose-graphene composite material is characterized in that the mass ratio of the lithium iron phosphate to the bacterial cellulose to the graphene is (1-5): (1-2): (1-2) according to the following steps:
step 1, weighing FeSO 4.7H 2O, Li3PO4 and citric acid according to the mass ratio of 3:3:1, taking deionized water as a solvent, uniformly mixing Li3PO4 and citric acid, adding graphene oxide, and performing ultrasonic dispersion uniformly to form a first solution;
in the step 1, mixing, stirring and dissolving Li3PO4 and citric acid in a beaker, then carrying out ultrasonic treatment on the solution, wherein the solution is colorless and transparent after full reaction, and the solution is colorless and transparent after full reaction;
step 2, adding the bacterial cellulose into an aqueous solution which is fully dissolved and dispersed with FeSO4 & 7H2O, carrying out high-speed cutting dispersion treatment and ultrasonic dispersion on the bacterial cellulose to form a bacterial cellulose-FeSO 4 & 7H2O dispersion solution, namely a second solution;
step 3, dropwise adding the first solution into the second solution to form uniformly dispersed lithium iron phosphate-bacterial cellulose-graphene composite dispersion liquid, putting the uniformly dispersed lithium iron phosphate-bacterial cellulose-graphene composite dispersion liquid into a hydrothermal reaction kettle, heating the mixture to 150-200 ℃ from the room temperature of 20-25 ℃ at the heating rate of 8-12 ℃/min, preserving heat for 4-8 hours for reaction, carrying out vacuum filtration after hydrothermal reaction to filter and filter a sample into a film, and obtaining a lithium iron phosphate-bacterial cellulose-graphene composite material film, and freeze-drying the film;
and 4, transferring the lithium iron phosphate-bacterial cellulose-graphene composite material film obtained in the step 3 into a tubular furnace to perform carbonization reduction treatment under the protection of argon flow and hydrogen flow, controlling the flow rates of the argon flow and the hydrogen flow in the whole carbonization process, wherein the argon flow rate is 180mL/min, the hydrogen flow rate is 10-20mL/min, and the temperature rise curve of the tubular furnace is set as follows: heating the sample to 300-350 ℃ from the room temperature of 20-25 ℃ at the heating rate of 2-5 ℃/min, heating the sample at the temperature for 1-2 hours at the constant temperature, heating the sample to 600-650 ℃ at the heating rate of 4-8 ℃/min, heating the sample at the temperature for 1.5-2.5 hours at the constant temperature, thus ensuring that the sample can be completely carbonized, and finally naturally cooling the sample to the room temperature of 20-25 ℃ to obtain a target product: lithium iron phosphate-bacterial cellulose-graphene composite material.
8. The method for preparing the lithium iron phosphate-bacterial cellulose-graphene composite material according to claim 7, wherein the mass ratio of the lithium iron phosphate to the bacterial cellulose to the graphene is (3-5): (1-2): (1-2).
9. The method for preparing the lithium iron phosphate-bacterial cellulose-graphene composite material according to claim 8, wherein the bacterial cellulose and the graphene are in an equal mass ratio.
10. The method for preparing the lithium iron phosphate-bacterial cellulose-graphene composite material as claimed in claim 7, wherein in the step 3, the temperature is raised to 180-200 ℃ from the room temperature of 20-25 ℃ at a heating rate of 8-12 ℃/min and the temperature is kept for 6-8h for reaction; the dripping is carried out at a constant speed of 5-10 ml per minute.
11. The method for preparing the lithium iron phosphate-bacterial cellulose-graphene composite material as claimed in claim 7, wherein in step 4, the flow rates of argon flow and hydrogen flow in the whole carbonization process are controlled, the flow rate of argon flow is 160mL/min, the flow rate of hydrogen is 15-20mL/min, and the temperature rise curve of the tube furnace is set as follows: heating the sample to 320-350 ℃ from 20-25 ℃ at the heating rate of 2-5 ℃/min, heating the sample at the temperature for 1-1.5 hours at the constant temperature, heating the sample to 620-650 ℃ at the heating rate of 4-8 ℃/min, heating the sample at the temperature for 2-2.5 hours at the constant temperature, and finally naturally cooling the sample to 20-25 ℃.
12. The application of the lithium iron phosphate-bacterial cellulose-graphene composite material as defined in claim 1 in preparation of a battery anode material.
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