CN110311110A - A kind of flexible lithium ion battery negative electrode material and its test method based on graphene - Google Patents
A kind of flexible lithium ion battery negative electrode material and its test method based on graphene Download PDFInfo
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- CN110311110A CN110311110A CN201910582112.5A CN201910582112A CN110311110A CN 110311110 A CN110311110 A CN 110311110A CN 201910582112 A CN201910582112 A CN 201910582112A CN 110311110 A CN110311110 A CN 110311110A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention discloses a kind of flexible lithium ion battery negative electrode material and its test method based on graphene, the following steps are included: the preparation of (1) precursor mixed solution: spreading liquid and be mixed in a certain proportion graphene alcohol dispersion liquid and red phosphorus ethyl alcohol point, ultrasonic disperse, red phosphorus/graphene oxide dispersion；(2) electrostatic spray;Precursor solution is taken with syringe, carries out spinning；(3) light wave restores: graphene-based red phosphorus composite membrane crude material being placed in micro-wave oven, soft graphite alkenyl red phosphorus compound film sheet cathode is obtained；(4) assembling and test of lithium ion half-cell: in the glove box of straight argon gas shielded, it is assembled into 2025 type button cell of CR, battery carries out constant current charge-discharge test, the method for ac impedance measurement, cyclic voltammetry.The composite material prepared by the method for the invention prepares cathode with height ratio capacity and longer service life cycle, can directly independently use as electrode.
Description
Technical field
The present invention relates to lithium ion battery negative material fields, more particularly to a kind of flexible lithium ion based on graphene
Cell negative electrode material and its test method.
Background technique
Lithium ion battery is a kind of secondary cell, rely primarily on lithium ion between a positive electrode and a negative electrode move back and forth work
Make, is made of the part such as anode, cathode, diaphragm, electrolyte, battery case, positive and negative anodes collector, safety valve, with traditional two
Primary cell (lead-acid battery, nickel-cadmium cell, nickel-metal hydride battery) is compared, and lithium ion battery has high operating voltage, specific energy and ratio
Many advantages, such as power is big, self discharge is small, have extended cycle life, memory-less effect, no pollution to the environment, meets today's society and is mentioned
The environmentally protective theory advocated.
Recently as the proposition of the concepts such as electronics clothes, flexible display screen, flexible mobile phone, lithium ion battery is wanted
Ask higher, these flexible electronic devices need lithium ion battery it is lighter, it is thinner, flexible and miniaturization.And the lithium being commercialized at present
The ion battery overwhelming majority is made of rigid material, needs to be added binder and metal collector, and the addition of metal collector
The weight that will increase electrode reduces the integral energy density of motor and influences the flexibility of electrode, while also implying that battery can not
It bears change in shape or bears battery failure after deformation, be unable to satisfy some flexible, implantable, wearable electronic product need
It wants.Therefore there is an urgent need to find some materials with special appearance and structure to prepare and production flexibility lithium ion battery.
Summary of the invention
The electrode material of traditional lithium ion battery is usually carbon-based material, silica-base material and transition metal oxide, is led to
It crosses and is mixed to form slurry with conductive agent and binder and coats on a current collector, active material holds very much during repeated deformation
Easily it is detached from collector.Therefore, the electrode design to make flexible battery gets rid of influence of the collector to battery performance, usually used
Itself there is electrode material flexible or use compound substance and flexible substrates.This kind of material predominantly has special appearance
The composite material of carbon material and carbon and other materials, including graphene, carbon nanotube and carbon fibre material.
Wherein, graphene is a kind of carbon material made of tightly packed as carbon atom with bi-dimensional cellular shape structure,
The advantage of structure and performance is mainly reflected in the following aspects: (1) excellent electron conduction, corrosion-resistant, is used as cathode material
Material or conductive agent, can be enhanced the electric conductivity of active material and collector；(2) have high-specific surface area, it is good chemically and thermally
Volume expansion is not present in mechanical stability in principle, and the graphene diffusion path of stable structure, micro-nano magnitude is short, charge and discharge
Fastly, good cycle；(3) excellent flexibility, be easily worked to form film, in flexible lithium ion battery, graphene both can be with
Negative electrode material is directly served as, and can serve as the collector of positive and negative pole material.But graphene is as lithium ion battery negative material
There are the problem of have: graphene size first is small, has high-specific surface area, and being easy to react with electrolyte, it is a large amount of to generate
SEI film leads to the irreversible capacity loss of battery；Secondly, graphene is easy to happen irreversible group during electrode cycle
It is poly-, cause battery capacity to decay.
Red phosphorus can react with lithium and generate Li3P, can theoretically provide the ultra-high capacity of 2596mAh/g, and have and close
The charging voltage (0.45V vs Li) and discharge voltage (0.9V vs Li) of reason, although phosphorous-based materials are with very high
Specific capacity, still, the grain diameter of red phosphorus itself are very big, as lithium ion battery negative material, irreversible capacity loss for the first time
Very much, in addition, the poorly conductive of red phosphorus also largely shortens moreover, itself also carries strong bulk effect
The service life of secondary cell.
It is in order to improve the energy density and power density of secondary cell, red phosphorus is compound with graphene, using red phosphorus as "
It is a kind of effective means for constructing ion diffusion duct in graphene molecules layer that spacer ", which is scattered between graphene sheet layer,.It utilizes
Graphene and red phosphorus prepare composite material, the thickness of the SEI film of optimizing surface, the intensity of enhancing base materials, and graphene-based nanometer is multiple
Condensation material retains double advantages of graphene and red phosphorus, effectively alleviates respective agglomeration, increases the specific surface area of material, increases
Active site increases electro-chemical activity, shortens ion transmission range, improves the electro-chemical activity of red phosphorus nanoparticle, generates association
Same benefit, the comprehensive chemical property for improving flexible storage reason battery.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: provide a kind of flexibility based on graphene
Lithium ion battery negative material, preparation method includes the following steps:
(1) preparation of graphene alcohol dispersion liquid
5g graphite is dissolved in 100ml N-Methyl pyrrolidone, mixed liquor is added in autoclave, in 150 ~ 210 DEG C
At a temperature of, 5h is heated, is stirred simultaneously；N-Methyl pyrrolidone mixed liquor is filtered, is cleaned with 100ml N-Methyl pyrrolidone,
Then 120 DEG C of dryings for 24 hours, then in N2Under protection, the calcination 2h at 400 DEG C.The micro crystal graphite for taking 0.5g to handle is added
Into dehydrated alcohol, ultrasound removing, natural subsidence takes upper layer, obtains graphene alcohol dispersion liquid；
(2) red phosphorus alcohol dispersion liquid is prepared:
A certain amount of red phosphorus is weighed, ball milling 16h in ball mill is placed in, crude red phosphorus is dissolved in dehydrated alcohol, ultrasound point
2h is dissipated, the alcohol dispersion liquid of red phosphorus is obtained.
(3) preparation of precursor solution:
Graphene alcohol dispersion liquid and red phosphorus ethyl alcohol point are spread liquid to mix with the ratio of 1:5 ~ 3:5, ultrasonic disperse 2h is obtained red
Phosphorus/graphene oxide dispersion.
(4) electrostatic spray:
Precursor solution 15mL is taken with syringe, under 16kV electrostatic potential, carries out spinning；Wherein, spinning is with needle diameter
0.2mm, spinning duration 10h.
(5) light wave restores:
Graphene-based red phosphorus composite membrane crude material is placed in micro-wave oven, microwave power is 800 ~ 900W, and irradiation time is
4min obtains soft graphite alkenyl red phosphorus compound film sheet cathode.
Further, a kind of lithium ion half-cell assembling side of the flexible lithium ion battery negative electrode material based on graphene
Method, it is characterised in that steps are as follows: by the battery cathode in being dried in vacuum oven, in the glove box of argon gas protection,
It is assembled into 2025 type button cell of CR, using the graphene-based red phosphorus composite material cathode of above-mentioned synthesis as test electrode, to electricity
Pole uses metal lithium sheet, and electrolyte is the LiPO of 1mol/L4F6, wherein solvent EC/DEC(volume ratio is 1:1), diaphragm uses
2320/ Celgard 2325/PE/PP of Celgard is compressed the battery seal installed to get assembling using cell package machine
The 2025 type button cell of CR of completion.
Wherein, argon gas is purity 99.999%, and water content is lower than 0.5ppm lower than 0.5ppm, oxygen content in glove box.
Further, a kind of survey of the lithium ion battery half-cell of the flexible lithium ion battery negative electrode material based on graphene
Method for testing, it is characterised in that: constant current charge-discharge test is carried out to the 2025 type button cell of CR being completed, exchange hinders
Anti- test, cyclic voltammetry, wherein constant current charge-discharge test condition is that charging and discharging currents are 50mA/g, and charge and discharge section is
0.01 ~ 3.0V, cycle-index are 30 times；Ac impedance measurement condition is that a-c cycle range is 10-105MHz, AC signal
Amplitude is 5mV；Cyclic voltammetry test condition is that scanning speed is 0.1mV/s, and voltage scan range is 0.01 ~ 3.0V.
Beneficial effect
The present invention a kind of flexible lithium ion battery negative electrode material and its test method, its advantages based on graphene is as follows:
1. large scale can be produced using electrostatic spray and preparation section is simple, had by the flexible electrode that electrostatic spray is synthesized
High-specific surface area, moreover, active material be uniformly distributed in the carbon fibers, have good mechanical strength.With electrostatic Spraying technique
The graphene-based negative electrode of lithium ion battery composite membrane of preparation can be directly used as negative electrode of lithium ion battery, and this method does not have to be added
There are the binder and conductive agent of pollution to environment, effectively raises the content of active material.
2. the flexible electrode that the negative electrode material for using method of the invention to prepare is constructed using graphene as substrate has excellent
Performance: 1. volume change of the active material in charge and discharge process can be effectively relieved in graphene, maintain the structure of electrode steady
It is fixed, be conducive to cyclical stability；2. the gap formed between graphene and active material is conducive to the transmission of ion；3. graphite
The reunion of the effective inhibitory activity particle of alkene energy, same active particle also can effectively inhibit the accumulation of graphene；4. three-dimensional
Netted graphene-structured can increase the electric conductivity of electrode, be conducive to its high rate performance.Red phosphorus and graphene oxide are compound also
After original, loose stereochemical structure is formed, the addition of phosphorus compensates for the defect of graphene, keeps structure more stable；Nano-grade size
Phosphorus particle be evenly distributed on graphene gap and surface.
3. the negative electrode material prepared using method of the invention, wherein red phosphorus: when graphene=2:5, compound film electrode exists
Specific capacity for the first time under 0.37A/g current density is 2540.6mAh/g, and coulombic efficiency is up to 94% for the first time；In 1A/g current density
Circulation 100 times, for coulombic efficiency close to 100%, capacity retention ratio is up to 95%.
4. the design of the flexible electrode has universality and large-scale production, can use same method, design and
Develop other high-performance composite and flexible electrodes.
Detailed description of the invention
Fig. 1 is button half-cell assembling schematic diagram；
Fig. 2 be graphite raw material and after solvent processing under different temperatures graphite XRD diagram: a) raw graphite, b) 150 DEG C, c)
180 DEG C, d) 210 DEG C；
Fig. 3 is the XRD of red phosphorus, graphene oxide, redox graphene membrane material and graphene-based red phosphorus composite film material
Figure；
Fig. 4 is the SEM figure of the graphene-based red phosphorus composite film material of different proportion: a) red phosphorus ethanol solution: graphene ethyl alcohol
Solution=1:5, b) red phosphorus ethanol solution: graphene ethanol solution=2:5, c) red phosphorus ethanol solution: graphene ethanol solution=3:
5；
Fig. 5 is (a) pure graphene film material, (b) red phosphorus: graphene=1:5 composite film material, (c) red phosphorus: graphene=
The composite film material of 2:5, (d) red phosphorus: graphene=3:5 composite film material is in 0.37A/g current density, preceding constant current three times
Charging and discharging curve figure；
Fig. 6 is pure graphene film material, red phosphorus: graphene=1:5 composite film material, red phosphorus: graphene=2:5 is compound
Membrane material, red phosphorus: graphene=3:5 composite film material is in 1A/g current density, 100 cycle lives and coulombic efficiency
Figure；
Fig. 7 is the AC impedance of the graphene-based red phosphorus composite film material of three kinds of different proportions of redox graphene membrane material
And its impedance fitted figure；
Fig. 8 is the cyclic voltammogram of graphene-based red phosphorus composite film material；
Fig. 9 is graphene-based red phosphorus composite membrane flexibility negative electrode material photomacrograph.
Specific embodiment
The preferred embodiments of the present invention will be described in detail with reference to the accompanying drawing, so that advantages and features of the invention energy
It is easier to be readily appreciated by one skilled in the art, so as to make a clearer definition of the protection scope of the present invention.
The flexible lithium ion battery negative electrode material based on graphene that the present invention provides a kind of, preparation method includes following
Step:
Step 1: a certain amount of graphite being dissolved in the N-Methyl pyrrolidone of 100ml, autoclave is added in mixed liquor
In, under certain temperature, heating is stirred simultaneously；By after heat treatment graphite and N-Methyl pyrrolidone mixed liquor filtering, use
N-Methyl pyrrolidone cleaning, it is dry, then in N2Under protection, calcination；
Step 2: taking the micro crystal graphite handled in a certain amount of step 1 to be added in dehydrated alcohol, ultrasound removing is naturally heavy
Drop, takes upper layer, obtains graphene alcohol dispersion liquid；
Step 3: a certain amount of red phosphorus is weighed, ball milling in ball mill is placed in, crude red phosphorus is dissolved in dehydrated alcohol, ultrasound
Dispersion, obtains the alcohol dispersion liquid of red phosphorus；
Step 4: the graphene ethanol solution of step 2 being mixed in certain proportion with the red phosphorus ethanol solution of step 3, ultrasound point
It dissipates, obtains red phosphorus/graphene oxide forerunner's dispersion liquid；
Step 5: forerunner's dispersion liquid in a certain amount of step 4 is taken with syringe, under certain electrostatic potential, carry out electrostatic
Mist；
Step 6: the graphene-based red phosphorus composite membrane crude material in step 5 is placed in micro-wave oven, microwave power be 800 ~
900W, irradiation time 4min obtain soft graphite alkenyl red phosphorus compound film sheet cathode.
Further, it is a kind of using it is above-mentioned it is a kind of based on graphene flexible lithium ion battery negative electrode material preparation lithium from
Sub- battery half cell assembling and test method, by the above-mentioned graphene-based red phosphorus compound film electrode being prepared in vacuum oven
Interior drying is assembled into 2025 type button cell of CR, in the glove box of argon gas protection with the graphene-based red phosphorus of above-mentioned synthesis
Composite material cathode uses metal lithium sheet as test electrode, to electrode, and electrolyte is the LiPO of 1mol/L4F6, wherein solvent
EC/DEC(volume ratio is 1:1), diaphragm uses 2320/ Celgard 2325/PE/PP of Celgard, will using cell package machine
The battery seal installed compresses, and battery carries out constant current charge-discharge test, the method for ac impedance measurement, cyclic voltammetry.
Wherein, argon gas is purity 99.999%, and water content is lower than 0.5ppm lower than 0.5ppm, oxygen content in glove box.
Wherein, it is 50mA/g that constant current charge-discharge test condition, which is charging and discharging currents, and charge and discharge section is 0.01 ~ 3.0V, is followed
Ring number is 30 times；Ac impedance measurement condition is that a-c cycle range is 10-105MHz, the amplitude of AC signal are 5mV；It follows
Ring voltammetry test condition is that scanning speed is 0.1mV/s, and voltage scan range is 0.01 ~ 3.0V.
Below with reference to embodiment 1 to embodiment to a kind of lithium ion battery negative material based on graphene of the invention and
Its test method is illustrated:
Embodiment 1
Graphene alcohol dispersion liquid is prepared:
5g graphite is dissolved in the N-Methyl pyrrolidone of 100ml, mixed liquor is added in autoclave, at 180 DEG C,
5h is heated, is stirred simultaneously；N-Methyl pyrrolidone mixed liquor is filtered, is cleaned with 100mlN- methyl pyrrolidone, in 120 DEG C
Lower drying for 24 hours, then in N2Under protection, the calcination 2h at 400 DEG C.The micro crystal graphite handled in 0.5g step 1 is taken to be added
Into dehydrated alcohol, ultrasound removing 10h, natural subsidence takes upper layer, obtains graphene alcohol dispersion liquid；
Red phosphorus alcohol dispersion liquid is prepared:
A certain amount of red phosphorus is weighed, ball milling 16h in ball mill is placed in, crude red phosphorus is dissolved in dehydrated alcohol, ultrasound point
2h is dissipated, the alcohol dispersion liquid of red phosphorus is obtained.
The preparation of precursor solution:
Graphene alcohol dispersion liquid and red phosphorus ethyl alcohol point are spread liquid to mix with the ratio of 2:5, ultrasonic disperse 2h obtains red phosphorus/oxygen
Graphite alkene dispersion liquid.
Electrostatic spray:
Precursor solution 15mL is taken with syringe, under 16kV electrostatic potential, carries out spinning；Wherein, spinning is with needle diameter
0.2mm, spinning duration 10h.
Light wave reduction:
Graphene-based red phosphorus composite membrane crude material is placed in micro-wave oven, microwave power is 800 ~ 900W, and irradiation time is
4min obtains soft graphite alkenyl red phosphorus compound film sheet cathode.
The assembling and test method of the lithium ion half-cell of flexible lithium ion battery negative electrode material preparation based on graphene:
By the above-mentioned graphene-based red phosphorus compound film electrode being prepared in being dried in vacuum oven, in the hand of straight argon gas shielded
In casing, it is assembled into 2025 type button cell of CR, using the graphene-based red phosphorus composite material cathode of above-mentioned synthesis as test electricity
Pole uses metal lithium sheet to electrode, and electrolyte is the LiPO of 1mol/L4F6, wherein solvent EC/DEC(volume ratio is 1:1), every
Film uses Celgard 2325, is compressed the battery seal installed using cell package machine, battery progress constant current charge-discharge test,
The method of ac impedance measurement, cyclic voltammetry.
Wherein, it is 50mA/g that constant current charge-discharge test condition, which is charging and discharging currents, and charge and discharge section is 0.01 ~ 3.0V, is followed
Ring number is 30 times；Ac impedance measurement condition is that a-c cycle range is 10-105MHz, the amplitude of AC signal are 5mV；It follows
Ring voltammetry test condition is that scanning speed is 0.1mV/s, and voltage scan range is 0.01 ~ 3.0V.
Embodiment 2-4
A kind of flexible lithium ion battery negative electrode material based on graphene that embodiment 2-4 is provided is compared with Example 1, different
Place is, in step 1, takes under different temperatures to raw graphite through the laggard horizontal high voltage kettle of N-Methyl pyrrolidone solvation
Heating reaction, different temperature parameters are shown in Table 1, remaining is consistent with embodiment 1.To the stone using treatment of different temperature
Ink does XRD analysis, as a result sees Fig. 2.
Comparative example 1
Comparative example 1 does XRD analysis without any processing for graphite raw material, as a result sees Fig. 2.
1 embodiment 2-4 of table different heating temperatures
| Embodiment | Solvation treatment conditions | Heating temperature/DEG C |
| Comparative example 1 | - | - |
| Embodiment 2 | Graphite/N-Methyl pyrrolidone | 150 |
| Embodiment 3 | Graphite/N-Methyl pyrrolidone | 180 |
| Embodiment 4 | Graphite/N-Methyl pyrrolidone | 210 |
Fig. 2 be graphite raw material and after NMP is handled at different temperatures graphite XRD as a result, XRD the result shows that: it is higher
At a temperature of handled with NMP after, the interlamellar spacing of graphite increased, and the interlamellar spacing increment value phase of expanded graphite is prepared with graphite
Than the interlamellar spacing of graphite increases to want much smaller after being handled with NMP, illustrates to be handled graphite with NMP not in graphite layers
It is inserted into any substance.
Embodiment 5-7
A kind of flexible lithium ion battery negative electrode material based on graphene that embodiment 5-7 is provided is compared with Example 1, different
Place is, in step 4 in the preparation of presoma dispersion solution, takes the red phosphorus ethanol solution and graphene ethyl alcohol of different proportion
Solution is prepared, and allocation ratio is shown in Table 2, remaining is consistent with embodiment 1.XRD points are carried out to the composite material sheet of preparation
Analysis, is as a result shown in Fig. 3.And electron microscope analysis is scanned to the composite material sheet of the three kinds of precursor solution matched preparations, as a result see
Fig. 4.
Comparative example 2-4
Comparative example 2-4 be the membrane material that pure graphene ethanol solution is prepared according to 1 method of embodiment and graphene oxide and
Red phosphorus raw material does XRD analysis, as a result sees Fig. 3.
The precursor solution that 2 embodiment 5-7 different proportion of table is prepared
| Embodiment | The precursor solution that different proportion is prepared |
| Comparative example 2 | Pure graphene film material |
| Comparative example 3 | Pure graphene oxide |
| Comparative example 4 | Pure red phosphorus |
| Embodiment 5 | Red phosphorus ethanol solution: graphene ethanol solution=1:5 |
| Embodiment 6 | Red phosphorus ethanol solution: graphene ethanol solution=2:5 |
| Embodiment 7 | Red phosphorus ethanol solution: graphene ethanol solution=3:5 |
Fig. 3 is that the graphene-based red phosphorus of pure graphene film material, graphene oxide, pure red phosphorus raw material and different proportion is compound
Membrane material is tested through XRD, structural characterization result.Through analyzing, graphene oxide is 10 in 2 θoThere is significant graphite oxide at left and right
Alkene characteristic peak, cutting edge of a knife or a sword shape is sharp, corresponding with graphene oxide d spacing 0.83nm, shows the oxidation stone prepared by the method for the present invention
Black alkene crystallinity is higher；After light-wave irradiation, 10o2 θ diffraction maximums at left and right disappear, and are about 26 in 2 θoOccur one wide
Peak shows that graphene oxide after light irradiates, has obtained reduced graphene；In addition, there are three characteristic diffraction peaks for red phosphorus simple substance, with stone
After black alkene is compound, three characteristic peaks without significant change, only graphene the diffraction maximum that 2 θ go out become it is wider show it is graphene-based red
Phosphorus composite material is in unformed shape.
Fig. 4 is red phosphorus ethanol solution: the graphene-based red phosphorus composite membrane of graphene ethanol solution=1:5,2:5,3:5 preparation
The scanning electron microscope (SEM) photograph of material.It can be seen from the figure that there are many loose laminated structure groups for graphene-based red phosphorus composite film material
At the typical fold shape characteristic of graphene is presented in surface, shows that, through electrostatic spray, light wave reduction forms loose three dimensional network
Shape structure, the insertion for being formed as lithium ion and abjection of this structure are provided convenience channel, and the embedding lithium of negative electrode material is increased
Amount.Moreover, in the graphene-based red phosphorus composite film material of three kinds of ratios, with the increase of red phosphorus content, the structure of composite membrane
It is increasingly looser, when the amount of red phosphorus increases to 60%, there is bulky grain to be formed in material, it turned out that be red phosphorus nanoparticle agglomerates
Body, and the presence of aggregate will lead to negative electrode material and generate volume expansion in charge and discharge process, to eventually fall out, contract significantly
Subtract the service life of lithium ion battery.To sum up, the optimum addition of red phosphorus is 40%, i.e. red phosphorus ethanol solution: graphene ethyl alcohol is molten
Liquid=2:5.
Embodiment 8-10
Embodiment 8-10 is using the inventive method of embodiment 1 as foundation, by the graphene-based red phosphorus composite membrane of three kinds of proportions in table 3
Material cathode assembling half-cell simultaneously carries out battery progress constant current charge-discharge test, ac impedance measurement, cyclic voltammetry.As a result
See Fig. 5-8.
Comparative example 5
Comparative example 5 is to assemble half-cell for redox grapheme material as cathode using the inventive method of embodiment 1 as foundation
And it carries out battery and carries out constant current charge-discharge test, ac impedance measurement, cyclic voltammetry.
3 embodiment 5-7 of table different negative electrode materials
| Embodiment | Different negative electrode materials |
| Comparative example 5 | Redox graphene |
| Embodiment 8 | Red phosphorus: graphene=1:5 |
| Embodiment 9 | Red phosphorus: graphene=2:5 |
| Embodiment 10 | Red phosphorus: graphene=3:5 |
In Fig. 5, in first time discharge process, red phosphorus: graphene=1:5,2:5,3:5 composite film material is successively provided
2375.8mAh/g, 2540.6mAh/g, 2059.8mAh/g height ratio capacity, for the first time coulombic efficiency be 71%, 94% and 68%, and not with
The compound redox graphene coulombic efficiency of red phosphorus only has 50%.And 2 times and the 3rd charging and discharging curve are almost overlapped in figure, this
Show to have formed stable SEI film by discharging for the first time, capacity therefore basicly stable, curve co-insides.To sum up, graphene-based red
Phosphorus composite membrane has superior storage rationality energy, wherein red phosphorus: graphene=2:5 chemical property is best.
Fig. 6 be under 1A/g current density, 100 circulation after, red phosphorus: graphene=1:5,2:5,3:5 composite film material
There are the height ratio capacity of 1429.6 mAh/g, 2683.1 mAh/g, 1189.5 mAh/g respectively, reversible capacity conservation rate is followed successively by
99%, 95%, 41%, and redox graphene film material capacity has decreased to 579.1 mAh/g, this shows graphene-based red phosphorus
Composite membrane has preferable electrochemistry and structural stability in recycling, but when red phosphorus content reaches 60%, the red phosphorus of reunion is received
Rice corpuscles is unfavorable for the improvement of performance.
Fig. 7 is electrochemical impedance spectrum analysis, shows red phosphorus and the compound defect for compensating for grapheme material of graphene, graphite
Alkenyl red phosphorus composite membrane shows lower charge transfer resistance than redox graphene film material, as the red of electron donor
Phosphorus easily ionizable goes out carrier, accelerates electronics transport, and red phosphorus: graphene=2:5 is best, shows appropriate red phosphorus and graphene
Synergistic effect increases electrical contact.
Fig. 8 is graphene-based red phosphorus composite film material under 0.5mV/s sweep speed, 3-0V range, first 5 times CV curves
Figure.It is the formation of SEI film, in cyclic process, in 1.0-1.75V as can be seen that occurring a small peak at 0.25-0.75V
There is reduction peak, but irreversible disappearance in place, then detects the oxidation peak at 1.25V, i.e., in lithium ion insertion red phosphorus.
Embodiment 11
Graphene-based red phosphorus compound film sheet in embodiment 1-10 is shot photo by embodiment 11.From fig. 9, it can be seen that graphite
Alkenyl red phosphorus compound film sheet can be with the bending of wide-angle, this just illustrates that the graphene-based red phosphorus compound film sheet being synthesized has one
Fixed flexibility and mechanical strength can look forward to the prospect that graphene-based red phosphorus compound film sheet is applied on flexible energy storage device.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification and accompanying drawing content is applied directly or indirectly in other relevant skills
Art field, is included within the scope of the present invention.
Claims (8)
1. a kind of preparation method of the flexible lithium ion battery negative electrode material based on graphene, it is characterised in that the negative electrode material
Preparation method comprise the steps of:
(1) preparation of graphene alcohol dispersion liquid
5g graphite is dissolved in 100ml N-Methyl pyrrolidone, N-Methyl pyrrolidone mixed liquor is prepared；By N- first
Micro crystal graphite is prepared after the filtering of base pyrrolidones mixed liquor, the micro crystal graphite for taking 0.5g to handle is added in dehydrated alcohol,
Ultrasound removing, natural subsidence take upper layer, obtain graphene alcohol dispersion liquid；
(2) red phosphorus alcohol dispersion liquid is prepared:
Red phosphorus is placed in ball milling 16h in ball mill, crude red phosphorus is dissolved in dehydrated alcohol, ultrasonic disperse 2h is obtained red
The alcohol dispersion liquid of phosphorus；
(3) preparation of precursor solution:
Graphene alcohol dispersion liquid is mixed, ultrasonic disperse 2h with red phosphorus alcohol dispersion liquid, obtains red phosphorus/graphene oxide dispersion
Liquid；
(4) electrostatic spray:
Precursor solution 15mL is taken with syringe, under 16kV electrostatic potential, carries out spinning；Wherein, spinning is with needle diameter
0.2mm, spinning duration 10h；
(5) light wave restores:
Graphene-based red phosphorus composite membrane crude material is placed in progress microwave irradiation processing in micro-wave oven, obtains soft graphite alkenyl
Red phosphorus compound film sheet cathode.
2. a kind of preparation method of flexible lithium ion battery negative electrode material based on graphene according to claim 1,
Be characterized in that, N-Methyl pyrrolidone mixed liquor is prepared by the following method in the step (1): it is anti-that high pressure is added in mixed liquor
It answers in kettle, at a temperature of 150 ~ 210 DEG C, heats 5h, stir simultaneously.
3. a kind of preparation method of flexible lithium ion battery negative electrode material based on graphene according to claim 2,
It is characterized in that, micro crystal graphite is prepared by the following method in the step (1): after the filtering of N-Methyl pyrrolidone mixed liquor, using
100ml N-Methyl pyrrolidone cleaning, then 120 DEG C of dryings for 24 hours, then in N2Under protection, the calcination 2h at 400 DEG C.
4. a kind of preparation method of flexible lithium ion battery negative electrode material based on graphene according to claim 1,
It is characterized in that, by the mass ratio of graphene alcohol dispersion liquid and red phosphorus alcohol dispersion liquid is 1:5 ~ 3:5 in the step (3).
5. a kind of preparation method of flexible lithium ion battery negative electrode material based on graphene according to claim 1,
It is characterized in that, the microwave power of the processing of microwave irradiation described in the step (5) is 800 ~ 900W, irradiation time 4min.
6. a kind of lithium ion half-cell assemble method of the flexible lithium ion battery negative electrode material based on graphene, feature exist
In steps are as follows for the assemble method: by the battery cathode in being dried in vacuum oven, in the glove box of argon gas protection
It is interior, it is assembled into 2025 type button cell of CR, using the graphene-based red phosphorus composite material cathode of above-mentioned synthesis as test electrode,
Metal lithium sheet is used to electrode, electrolyte is the LiPO of 1mol/L4F6, wherein solvent EC/DEC volume ratio is 1:1, and diaphragm uses
2320/ Celgard 2325/PE/PP of Celgard is compressed the battery seal installed to get assembling using cell package machine
The 2025 type button cell of CR of completion.
7. half electricity of a kind of lithium ion battery of the flexible lithium ion battery negative electrode material based on graphene as claimed in claim 6
Pond assemble method, it is characterised in that: argon gas is purity 99.999%, and water content is lower than lower than 0.5ppm, oxygen content in glove box
0.5ppm。
8. a kind of test method of the lithium ion battery half-cell of the flexible lithium ion battery negative electrode material based on graphene, special
Sign is: carrying out constant current charge-discharge test, ac impedance measurement, circulation to the 2025 type button cell of CR being completed
Volt-ampere test, wherein constant current charge-discharge test condition is that charging and discharging currents are 50mA/g, and charge and discharge section is 0.01 ~ 3.0V, is followed
Ring number is 30 times；Ac impedance measurement condition is that a-c cycle range is 10-105MHz, the amplitude of AC signal are 5mV；It follows
Ring voltammetry test condition is that scanning speed is 0.1mV/s, and voltage scan range is 0.01 ~ 3.0V.
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