CN110010961A - A kind of PVDF-HFP/PMMA/PVP gelatin polymer and the preparation method and application thereof - Google Patents
A kind of PVDF-HFP/PMMA/PVP gelatin polymer and the preparation method and application thereof Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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Abstract
The present invention provides a kind of PVDF-HFP/PMMA/PVP gelatin polymers and the preparation method and application thereof, belong to technical field of polymer.Gelatin polymer of the invention is prepared by PVDF-HFP, PMMA, PVP and solvent；The PVDF-HFP/PMMA/PVP gelatin polymer has porous network structure.PVP of the invention has the characteristics that good biocompatibility and film forming, caking property, while can improve the crystallinity of gel rubber system, promotes the chemical property of polymer.Itself and PMMA, PVDF-HFP collective effect, are capable of forming reticular structure, improve the chemical property of gelatin polymer.Embodiment statistics indicate that: capacity retention ratio reaches 87.6% after half-cell that inventive gel polymer is assembled into recycles 100 times；In the generation that has almost no change after heavy-current discharge, it is still able to maintain preferable performance, can be applied to lithium battery.
Description
Technical field
The present invention relates to technical field of polymer more particularly to a kind of PVDF-HFP/PMMA/PVP gelatin polymer and its
Preparation method and application.
Background technique
Affinity between polymer and solvent is to influence gel polymer electrolyte film mechanical performance, room-temperature ion conductance
The key factor of rate and solvent liquid-keeping property.The polymer of high-affinity conductivity at room temperature with higher and solvent protect liquid
Ability, but mechanical performance is poor；And the polymer of low-affinity has high mechanical strength, but it forms easy hair when gel
Raw microphase-separated；And gel polymer electrolyte chemical property is poor.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of PVDF-HFP/PMMA/PVP gelatin polymer and its preparations
Method and application, PVDF-HFP/PMMA/PVP gelatin polymer provided by the invention have excellent chemical property, thermostabilization
Property, it can be applied to lithium battery.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of PVDF-HFP/PMMA/PVP gelatin polymers, by including that following raw material is prepared:
PVDF-HFP, PMMA, PVP and solvent, the mass ratio of described PVDF-HFP, PMMA and PVP are 5~9:5~9:1；The PVDF-
HFP/PMMA/PVP gelatin polymer has porous network structure.
Preferably, the mass ratio of the PVDF-HFP and PMMA is 1:1.
Preferably, the mass ratio of described PVDF-HFP, PMMA and PVP are 7:7:1.
Preferably, the solvent includes acetone and DMF；The volume ratio of the acetone and DMF are 3:1.
The present invention also provides the preparation method of PVDF-HFP/PMMA/PVP gelatin polymer described in above-mentioned technical proposal,
The following steps are included:
After PVDF-HFP, PMMA, PVP and solvent are mixed, film forming removes solvent, obtains the gelatin polymer.
Preferably, the mixed temperature is 55~65 DEG C, time 5h.
Preferably, the temperature for removing solvent is 60~80 DEG C, time 12h.
The present invention also provides PVDF-HFP/PMMA/PVP gelatin polymers described in above-mentioned technical proposal in field of lithium
In application.
The present invention provides a kind of PVDF-HFP/PMMA/PVP gelatin polymers, by including that following raw material is prepared:
PVDF-HFP, PMMA, PVP and solvent, the mass ratio of described PVDF-HFP, PMMA and PVP are 5~9:5~9:1, the PVDF-
HFP/PMMA/PVP gelatin polymer has porous reticular structure.PVP is a kind of unformed high molecular polymer, is had fine
Biocompatibility and film forming, caking property the features such as, while the crystallinity of gel rubber system can be improved, promote polymer electrification
Performance is learned, the polymer P VDF-HFP collective effect with PMMA and with low-affinity is capable of forming reticular structure, makes to polymerize
Object has excellent chemical property.Embodiment statistics indicate that: gelatin polymer provided by the invention have excellent imbibition
Rate, mechanical strength and thermal stability；For electrochemical stability window in 4.5V or more, ionic conductivity is 1.260~6.421mS/cm；
After 100 circulations, the half-cell that gelatin polymer is assembled into remains highest specific discharge capacity, and specific discharge capacity declines
Subtract minimum, capacity retention ratio reaches 87.6%；Gelatin polymer discharge under high magnification special capacity fade minimum, through excessive
Have almost no change generation after current discharge, is still able to maintain preferable performance, illustrates the gelatin polymer and electrode material
Interface stability is preferable.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of 1 gained film of comparative example 1, comparative example 2 and embodiment；
Fig. 2 is the scanning electron microscope (SEM) photograph of film obtained by Examples 1 to 5；
Fig. 3 is the TGA curve of film obtained by Examples 1 to 5；
Fig. 4 is the electrochemical window of film obtained by Examples 1 to 5；
Fig. 5 is the AC impedance spectroscopy of film obtained by Examples 1 to 5；
In Fig. 6, figure (a) is that charge-discharge magnification is 0.2C, film assembling obtained by Examples 1 to 5 under the conditions of temperature is 25 DEG C
At LiCoO2The first charge-discharge curve graph of/GPE/Li half-cell；Figure (b) is what film obtained by Examples 1 to 5 was assembled into
LiCoO2Cycle performance of/GPE/Li the half-cell under 0.2C multiplying power；
Fig. 7 is the LiCoO that film obtained by Examples 1 to 5 is assembled into2Electric discharge of/GPE/Li the half-cell under different multiplying
The test result of specific capacity.
Specific embodiment
The present invention provides a kind of PVDF-HFP/PMMA/PVP gelatin polymers, by including that following raw material is prepared:
PVDF-HFP, PMMA, PVP and solvent, the mass ratio of described PVDF-HFP, PMMA and PVP are 5~9:5~9:1；The PVDF-
HFP/PMMA/PVP gelatin polymer has porous network structure.
In the present invention, the mass ratio of the PVDF-HFP and PMMA is preferably 1:1.In the present invention, the PVDF-
The mass ratio of HFP, PMMA and PVP are 5~9:5~9:1, preferably 6~8:6~8:1, further preferably 7:7:1.In this hair
In bright, the solvent preferably includes DMF and acetone；The volume ratio of the DMF and acetone is preferably 1:3.The present invention is to described molten
The dosage of agent is not specifically limited.The present invention to the source of described PVDF-HFP, PMMA and PVP without limitation, using this field
Commercial product known to technical staff.
In the present invention, PVP is a kind of unformed high molecular polymer, have good biocompatibility and film forming,
The features such as caking property, while can improve the crystallinity of gel rubber system, promotes polymer electrochemical performance, and PMMA and has
The polymer P VDF-HFP collective effect of low-affinity, is capable of forming reticular structure, and gelatin polymer is made to have excellent electrification
Learn performance.
The present invention also provides the preparation method of PVDF-HFP/PMMA/PVP gelatin polymer described in above-mentioned technical proposal,
The following steps are included:
After PVDF-HFP, PMMA, PVP and solvent are mixed, film forming removes solvent, obtains the gelatin polymer.
In the present invention, the mixed temperature is preferably 55~65 DEG C, and further preferably 60 DEG C；Time is preferably
5h.In the present invention, the mixing preferably carries out under stirring conditions；The revolving speed of the stirring is preferably 200~600rpm.
After mixing, mixed solution is further preferably stood de-bubble by the present invention.
The present invention is not specifically limited the mode of the film forming, is using thin film-forming method well known to those skilled in the art
It can.In the present invention, it is preferably 15~30 μm that film forming, which obtains the thickness of film,.
In the present invention, the temperature for removing solvent is preferably 60~80 DEG C, and further preferably 70 DEG C；Time is preferred
For 12h.In the present invention, the removal of solvent DMF and acetone makes gelatin polymer have good pore structure.Further, third
Ketone is from film to the very fast of external diffusion, and DMF diffusion is relatively slow, under the two collective effect, film is caused to be formed after drying
Porous structure.
The present invention also provides PVDF-HFP/PMMA/PVP gelatin polymers described in above-mentioned technical proposal in field of lithium
In application.In the present invention, the lithium battery preferably includes ferric phosphate lithium cell or lithium manganate battery.The present invention is to described
The application mode of PVDF-HFP/PMMA/PVP gelatin polymer is not specifically limited, and those skilled in the art are according to actual needs
It is selected, it specifically such as, can be using big block-like gelatin polymer or the gelatin polymer of film-form.The present invention
Dosage of the PVDF-HFP/PMMA/PVP gelatin polymer in application is not specifically limited, those skilled in the art are according to reality
Border is selected.
Since PVDF-HFP/PMMA/PVP gelatin polymer of the invention has excellent pattern, stability and conductivity
Equal electric properties can be applied to lithium battery as electrolyte.
Below with reference to embodiment to PVDF-HFP/PMMA/PVP gelatin polymer provided by the invention and preparation method thereof with
Using being described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
First with acetone/DMF (volume ratio 3:1) for solvent, then weigh PMMA, PVDF- that quality proportioning is 5:5:1
HFP and PVP is added in single neck flask, thick liquid constant temperature stirring 5h transparent to solution at 60 DEG C；It stands and removes degassing
Bubble, coating film forming, 40s are placed in a vacuum drying oven 60 DEG C of dry 12h later, obtain PVDF-HFP/PMMA/ on a glass
PVP film.
Embodiment 2
Similar to Example 1, difference is only that the mass ratio of described PMMA, PVDF-HFP and PVP are 6:6:1.
Embodiment 3
Similar to Example 1, difference is only that the mass ratio of described PMMA, PVDF-HFP and PVP are 7:7:1.
Embodiment 4
Similar to Example 1, difference is only that the mass ratio of described PMMA, PVDF-HFP and PVP are 8:8:1.
Embodiment 5
Similar to Example 1, difference is only that the mass ratio of described PMMA, PVDF-HFP and PVP are 9:9:1.
Comparative example 1
Similar to Example 1, difference, which is only that, is added without PMMA and PVP.
Comparative example 2
Similar to Example 1, difference, which is only that, is added without PVDF-HFP and PVP.
Performance test
1, infrared spectrum analysis (FT-IR)
Fig. 1 is 1 gained PVDF-HFP film of comparative example, 1 gained PVDF- of 2 gained PMMA film of comparative example and embodiment
The infrared spectrum of HFP/PMMA/PVP film.In the spectrogram of 1 gained PVDF-HFP/PMMA/PVP film of embodiment it can be seen that
It is in 2950cm-1The peak at place is CH2And CH3The vibration absorption peak of middle C-H, 1677cm-1, 1730cm-1Place is the C=O on PMMA
Vibration absorption peak, the classical absorption peak of PVDF-HFP is 1406cm respectively-1Place-CH2Bending vibration caused by absorption peak and
1072cm-1Locate the vibration absorption peak of C-C, the classical absorption peak of PVP is 1670cm-1The vibration absorption peak of the C=O at place and
2950cm-1The vibration absorption peak and 1290cm of the C-H at place-1The vibration absorption peak of the C-N at place, 1670cm-1And 2950cm-1's
Peak is overlapped with other peaks；Illustrate to be blended and work well.
2, morphology analysis (SEM)
The scanning electron microscope (SEM) photograph of PVDF-HFP/PMMA/PVP film obtained by Examples 1 to 5 is as shown in Fig. 2, wherein scheme (a), figure
(b), scheme (c), figure (d) and figure (e) and respectively represent embodiment 1, embodiment 2, embodiment 3, embodiment 4,5 gained film of embodiment
Scanning electron microscope (SEM) photograph.As seen from Figure 2, PVDF-HFP/PMMA/PVP film obtained by Examples 1 to 5 has good pore structure,
These stomatas are in film forming procedure caused by the volatilization of acetone and DMF, i.e., acetone is from film to the very fast of external diffusion, and DMF expands
Scattered is relatively slow, under the two collective effect, film is caused to form porous structure after drying.
When the mass ratio of PVDF-HFP, PMMA and PVP are 5:5:1, gained film is almost without hole, but with PVP
The increase of content, aperture are being gradually increased, and the quantity in hole is gradually decreasing；When the mass ratio of PVDF-HFP, PMMA and PVP are 7:
When 7:1, gained film generate be evenly distributed, 0.1 μm or so of macropore of substantial amounts；And work as PVDF-HFP, PMMA and PVP
Mass ratio be 8:8:1 when, gained film have maximum aperture；But when proportion is 9:9:1, aperture reduces and has few portion
The raw closure of distribution.Large aperture can receive more liquid electrolytes, but can reduce film and act on the holding of electrolyte, very
To the mechanical strength for influencing film；And small-bore is unfavorable for the transmission of lithium ion, therefore, it is necessary to control various substances in film
Proportion in a certain range, make gained the existing suitable imbibition rate of film have certain mechanical strength again.
3, TGA is analyzed
TGA analysis, atmospheric condition N are carried out using SDT Q600 type thermogravimetric analyzer herein2, 10 DEG C of heating rate/
Min, temperature range is from room temperature to 600 DEG C.
The TGA curve of PVDF-HFP/PMMA/PVP film obtained by Examples 1 to 5 is as shown in Figure 3；Wherein figure (b) is figure
(a) partial enlarged view.As can be seen from Figure 3: in addition to the fraction water or dissolvent residual quilt in the film at 100 DEG C or so
Evaporation is outer, and the film of different quality proportion is all just to start to decompose at 220 DEG C or more.PVDF-HFP/PMMA/PVP (5:5:1) exists
224 DEG C or so the beginning first steps are decomposed, and 437 DEG C of beginning second steps decompose, and final conservation rate is 20.5%.With PVP content
Increase, the decomposition temperature first increases and then decreases of blend film, highest decomposition temperature is the 323 of PVDF-HFP/PMMA/PVP (7:7:1)
DEG C, final conservation rate is 21.4%.The decomposition temperature of the PVDF-HFP/PMMA/PVP film of preparation polymerize higher than lithium ion battery
Object electrolyte real work maximum temperature (150 DEG C) illustrates that PVDF-HFP/PMMA/PVP film has excellent thermal stability,
It can satisfy lithium ion battery actual use demand.
4, electrochemical window is analyzed
The battery that positive and negative anodes are respectively stainless steel substrates and lithium piece is assembled into after film is infiltrated electrolyte.Using
PGSTAT302N type electrochemical workstation carries out linear sweep voltammetry and is tested, and test voltage is 2~6V, and sweep speed is
0.5mV·s-1。
Electrochemical stability window, that is, electrolyte can be stabilized in certain operating voltage range, for polymer lithium
For ion battery, operating voltage tends to reach 4.5V, this shows that the electrochemical stability window of polymer dielectric is wanted
Reach 4.5V or more.Fig. 4 is the electrochemical window of film obtained by Examples 1 to 5, wherein figure (b) is the partial enlargement for scheming (a)
Figure.It can be seen from figure 4 that electrochemical reaction does not occur between 2.0V to 4.55V for 1 gained film of embodiment, at 4.55V
There is a phenomenon where electric currents to increase suddenly, then its electrochemical stability window is 4.55V.The PVDF-HFP/PMMA/ of different quality proportion
The sequence of the electrochemical window of PVP film is arranged successively: embodiment 5 (9:9:1) (4.45V) < embodiment 1 (5:5:1)
2 (6:6:1) (4.9V) < embodiment 3 (7:7:1) (5.0V) of (4.55V) < embodiment 4 (8:8:1) (4.78V) < embodiment.
5, ionic conductivity
Use perforating press that film obtained by Examples 1 to 5 is cut into disk that diameter is 16mm as diaphragm, in vacuum glove box
In, stainless steel substrates/polymer dielectric/stainless steel substrates obstruction battery is assembled into after diaphragm is infiltrated electrolyte.Using
PGSTAT302N type electrochemical workstation carries out ac impedance measurement, and test frequency is 0.01Hz~105Hz, the ion-conductance of diaphragm
Conductance is calculated by formula (1):
In formula, σ is ionic conductivity (Scm-1)；The thickness (μm) of d expression battery diaphragm；R is the bulk resistance of diaphragm
(Ω)；S is the area (cm of stainless steel electrode2)。
The AC impedance spectroscopy of the resulting PVDF-HFP/PMMA/PVP film of Examples 1 to 5 is shown in Fig. 5, by Fig. 5
It is found that PMMA, PVDF-HFP and PVP quality proportioning are the PVDF-HFP/ of 5:5:1,6:6:1,7:7:1,8:8:1,9:9:1
The bulk resistance of PMMA/PVP film is respectively 6.241 Ω, 2.183 Ω, 1.201 Ω, 3.529 Ω, 5.384 Ω.According to formula (1)
The ionic conductivity that can find out film obtained by Examples 1 to 5 is calculated, the results are shown in Table 1: as can be seen from Table 1: different quality
The ionic conductivity of the PVDF-HFP/PMMA/PVP film of proportion is 1.260mS/cm, 3.532mS/cm, 6.421mS/ respectively
Cm, 2.157mS/cm, 1.414mS/cm.
The ionic conductivity of PVDF-HFP/PMMA/PVP film obtained by 1 Examples 1 to 5 of table
6, cycle performance is tested
By positive pole material of lithium cobalt acid, conductive agent acetylene black, binder PVDF solution (solvent is 1-Methyl-2-Pyrrolidone)
According to mass ratio be 8:1:1, by slurry agitation half an hour to be uniformly mixed jelly.The slurry spreader stirred evenly is equal
It is even to be coated in aluminium foil rough surface, and coated aluminium foil is placed in 100 DEG C of vacuum ovens dry 2h, then perforating by punching system
Obtain lithium cobaltate cathode piece.In the vacuum glove box of argon atmosphere, in the electrolytic solution by the film infiltration after punching, then with punching
Lithium cobaltate cathode piece behind hole is anode, and lithium piece is cathode, is assembled into LiCoO2/ polymer dielectric/lithium piece half-cell.It will
After assembled battery places 12h, charge and discharge is carried out to battery using the new Weir Electronics Co., Ltd. battery test system in Shenzhen
Electrical property and cycle performance test, 25 DEG C of test temperature, 2.7~4.20V of voltage range, charging current 0.2C, cycle-index
It is 100 times.
In Fig. 6, figure (a) is that charge-discharge magnification is 0.2C, the PVDF-HFP/ that different quality matches under the conditions of temperature is 25 DEG C
The LiCoO that PMMA/PVP film is assembled into2The first charge-discharge curve graph of/GPE/Li half-cell schemes (a) the results show that PVDF-
HFP, PMMA and PVP quality proportioning are respectively the LiCoO of the film assembling of 5:5:1,6:6:1,7:7:1,8:8:1 and 9:9:12/
The initial charge specific capacity of GPE/Li half-cell is successively: 165.6mAh/g, 170.8mAh/g, 173.1mAh/g, 175.3mAh/
G, 160.8mAh/g, corresponding first discharge specific capacity is respectively: 156.2mAh/g, 158.7mAh/g, 166.2mAh/g,
161.2mAh/g, 153.8mAh/g, from above-mentioned data it is found that the first charge-discharge capacity of film is first with the increase of PVP content
It is reduced after increase, this may be to increase the viscosity of solution because the ratio of PVP is excessive, solvent is caused to be difficult to wave from film
It issues, so that porosity, ionic conductivity decline.
In Fig. 6, figure (b) shows the LiCoO that the PVDF-HFP/PMMA/PVP film of different quality proportion is assembled into2/GPE/
Cycle performance of the Li half-cell under 0.2C multiplying power.It can be concluded that, tested in 100 charge and discharge cycles by test result
In, quality proportioning is that the half-cell of PVDF-HFP/PMMA/PVP (7:7:1) assembling remains highest specific discharge capacity,
And specific discharge capacity decaying is minimum, and capacity retention ratio reaches 87.6%.The appearance and film of other quality proportionings not only discharges
Smaller than 7:7:1 in amount, it is low that the conservation rate of capacity also compares its.The PVDF- of quality proportioning 5:5:1,6:6:1,8:8:1,9:9:1
The LiCoO of HFP/PMMA/PVP film assembling2First discharge specific capacity of/GPE/Li the half-cell under 0.2C multiplying power is successively:
156.2mAh/g, 158.7mAh/g, 161.2mAh/g, 153.8mAh/g, after 100 circulations, capacitance conservation rate
Respectively 57.8%, 80.9%, 86.1%, 72.7%.To sum up, the PVDF-HFP/PMMA/PVP film phase of quality proportioning 7:7:1
Relatively it is suitable as the diaphragm material of lithium ion battery.
7, high rate performance
After carrying out the assembled battery placement 12h of cycle performance test, using new Weir Electronics Co., Ltd., Shenzhen
Battery test system, respectively at 0.2C, 0.5C, 1C, 2C to battery carry out constant current charge-discharge test, voltage range 2.7~
4.20V, multiplying power discharging repeat charge-discharge test under 0.2C after the completion, and cycle-index is respectively 5 times, and 25 DEG C of test temperature.
Multiplying power discharging ability can reflect the ion transport capability and electrolyte/electrode interface property of polymer.Fig. 7 is
The LiCoO that the PVDF-HFP/PMMA/PVP film of different quality proportion is assembled into2/ GPE/Li half-cell is under different multiplying
The test result of specific discharge capacity.0.2C multiplying power is carried out again passing through 0.2C, 0.5C, 1C after the electric discharge of 2C and 5C different multiplying
Electric discharge.Experimental result clearly demonstrates that the specific discharge capacity of PVDF-HFP/PMMA/PVP film half-cell is dropped with the increase of multiplying power
It is low.As seen from the figure, the PVDF-HFP/PMMA/PVP film of quality proportioning 7:7:1 discharge under high magnification special capacity fade minimum,
And still can reach 160.4mAh/g when carrying out 0.2C multiplying power discharging again, it is maintained with 0.2C multiplying power discharging before compared to specific capacity
99.5%, it is lost considerably less.In the generation that has almost no change after heavy-current discharge, it is still able to maintain preferable performance, is said
The interface stability of the bright gelatin polymer and electrode material is preferable.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of PVDF-HFP/PMMA/PVP gelatin polymer, which is characterized in that by including that following raw material is prepared: PVDF-
HFP, PMMA, PVP and solvent, the mass ratio of described PVDF-HFP, PMMA and PVP are 5~9:5~9:1；The PVDF-HFP/
PMMA/PVP gelatin polymer has porous network structure.
2. gelatin polymer according to claim 1, which is characterized in that the mass ratio of the PVDF-HFP and PMMA is 1:
1。
3. gelatin polymer according to claim 1 or 2, which is characterized in that the matter of described PVDF-HFP, PMMA and PVP
Amount is than being 7:7:1.
4. gelatin polymer according to claim 1, which is characterized in that the solvent includes acetone and DMF；The acetone
Volume ratio with DMF is 3:1.
5. the preparation method of any one of Claims 1 to 4 PVDF-HFP/PMMA/PVP gelatin polymer, which is characterized in that
The following steps are included:
After PVDF-HFP, PMMA, PVP and solvent are mixed, film forming removes solvent, obtains the gelatin polymer.
6. preparation method according to claim 5, which is characterized in that the mixed temperature is 55~65 DEG C, and the time is
5h。
7. preparation method according to claim 5, which is characterized in that the temperature for removing solvent is 60~80 DEG C, when
Between be 12h.
8. any one of any one of Claims 1 to 4 PVDF-HFP/PMMA/PVP gelatin polymer or claim 5~7 institute
State the application of PVDF-HFP/PMMA/PVP gelatin polymer that preparation method is prepared in field of lithium.
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Application publication date: 20190712 |