CN104852013B - A kind of preparation method of the three-diemsnional electrode pole piece based on aqueous binders - Google Patents
A kind of preparation method of the three-diemsnional electrode pole piece based on aqueous binders Download PDFInfo
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- CN104852013B CN104852013B CN201510117274.3A CN201510117274A CN104852013B CN 104852013 B CN104852013 B CN 104852013B CN 201510117274 A CN201510117274 A CN 201510117274A CN 104852013 B CN104852013 B CN 104852013B
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Abstract
The present invention proposes a kind of three-diemsnional electrode pole piece and preparation method thereof based on aqueous binders.Slurry will be mixed up according to a certain percentage with aqueous binders, conductive agent and active material coated in three-dimensional porous metal collector, and the three-diemsnional electrode pole piece of lithium ion battery is gone out by operation preparations such as drying, rolling, slice or further carbonizations.The present invention has cheap, from a wealth of sources, the advantages such as environmental-friendly as binder using water-soluble organic macromolecule material.The three-diemsnional electrode pole piece that the present invention prepares has porous three-dimensional structure, and such three-dimensional structure is conducive to the infiltration of electrolyte, improves the interface compatibility of electrolyte and active material, effectively improves the discharge-rate characteristic of battery.The configuration of the present invention is simple, preparation process are easy, and process is easy to accomplish.
Description
Technical field
The present invention relates to a kind of preparation methods of three-diemsnional electrode pole piece, and in particular to a kind of three-dimensional based on aqueous binders
The preparation method of electrode plates.
Background technique
As consumer electronics demand grows steadily, hybrid vehicle and pure electric automobile fast development and new energy are simultaneously
Net power project pace of construction is accelerated, and high-performance energy-storage battery becomes one of the core technology greatly developed.Wherein, lithium ion
The advantages that battery is because of its high voltage, large capacity, cycle performance are good, low pollution has a high potential in fields such as distributed power generation energy storage.
With the continuous promotion of lithium ion battery cost performance, lithium electricity replaces the trend of the conventional batteries such as plumbic acid, nickel-metal hydride battery increasingly apparent.
The performance of lithium ion battery and the performance of active material and electrode chip architecture are closely related.Currently, common lithium-ion electric
Pond positive electrode has cobalt acid lithium, LiFePO4 and ternary material, and negative electrode material mainly has graphite, lithium titanate, silica-base material, transition
Largely all there are electronic conductivity difference, some materials in metal oxide, above-mentioned active material (in addition to graphite cathode)
Expect (for example, silica-base material and transition metal material) the problem of there is also bulk effects.Therefore, Novel electric pole piece knot is designed and developed
The bulk effect that structure is conducive to that certain inhibitory activity material can also be played while improving the electronic conductance of pole piece has centainly
Realistic meaning.
Common positive/negative collector is aluminium/copper foil in business, and the manufacture craft of pole piece is will to contain conductive agent, activity
The slurry of substance is adhered to the surface of copper foil by binder, and rolling obtains electrode plates under a certain pressure after drying.It is this
The interfacial property of electrode largely affects the charge-discharge performance of electrode slice.Simultaneously as this foil-like collector
Surface is relatively smooth, and some biggish active materials of bulk effect are easy from foil-like collector in charge and discharge process
Removing.CN 102437313A patent, as electrode current collecting body, uses solid phase using the foam copper or nickel foam of three-dimensional porous structure
The method of filling and compression moulding has prepared a kind of negative electrode for high-power metal lithium battery.This method is conducive to powder lithium
It directly contacts with electrode current collecting body but is bonded fastness and remain to be further improved.There is document report by the compound of graphene and silicon
Object is attached to the chemical property for being also beneficial to improve electrode slice on three-dimensional foam graphite network, but relative to foam copper or nickel foam
For, the price of foamy graphite net is higher, and ductility is insufficient.(Adv.Mater.2013,25,4673–4677).
Summary of the invention
It is provided a kind of based on aqueous binders it is an object of the invention to overcome the shortcomings of the prior art place
Three-diemsnional electrode pole piece preparation method, the present invention also provides using this method preparation three-diemsnional electrode pole piece, and application thereof.
To achieve the above object, a kind of technical solution taken: system of the three-diemsnional electrode pole piece based on aqueous binders
Preparation Method the described method comprises the following steps:
(1) aqueous binders, conductive agent and active material are mixed, after obtaining mixture, with solvent by the mixture
It is modulated into slurry, then the foam-metal current collector body of three-dimensional porous structure is soaked in the slurry, is taken out after complete wetting
The three-dimensional porous metal collector；
(2) three-dimensional porous metal collector obtained in step (1) is obtained described three after drying, rolling, slice
Tie up electrode plates.
Preferably, in the step (1) aqueous binders be water-soluble organic macromolecule material aqueous solution.
Preferably, in the step (1) water-soluble organic macromolecule material be chitosan derivatives, carboxymethyl cellulose,
At least one of alginate, water-soluble terpene resin, aqueous polyurethane.
Preferably, conductive agent is conducting polymer, conductive carbon powder, acetylene black, graphene and conductive silver in the step (1)
At least one of powder；The foam-metal current collector body of three-dimensional porous structure is foam copper, nickel foam and foam in the step (1)
One of aluminium；Active material is LiFePO4, cobalt acid lithium, LiMn2O4, nickel cobalt manganese, nickel ion doped, phosphoric acid in the step (1)
At least one of nickel lithium, cobalt phosphate lithium, lithium manganese phosphate and rich lithium solid solution cathode material or the active material are silicon
In powder, graphite, lithium titanate, metal oxide negative electrode material, tinbase composite negative pole material and silicon substrate composite negative pole material at least
It is a kind of.Preferably, conducting polymer is poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid), gathers in the step (1)
At least one of aniline and polypyrrole.It is highly preferred that in the step (1) conductive agent be conducting polymer and conductive carbon powder,
The mixture of one or more of acetylene black, graphene and conductive silver powder.In the present invention when selection negative electrode material is as work
Property substance when, the three-diemsnional electrode pole piece prepared is three-dimensional negative electricity pole piece；When selecting positive electrode as active material, system
Standby three-diemsnional electrode pole piece out is three-dimensional anode electrode piece.
Preferably, in the step (1) on the basis of the total weight of the mixture, weight shared by the active material
Percentage is 70%~90%, and the aqueous binders account for 1%~10%, shared by the conductive agent
Weight percent is 9%~20%；The viscosity of slurry is 1000cps~5000cps in the step (1).Preferably, the step
Suddenly solvent described in (1) is water.
Preferably, it is carbonized under inert gas shielding atmosphere after slice in the step (2), obtains the three-diemsnional electrode pole
Piece.Aqueous binders are carbonized to form support carbon-coating in above process, are conducive to the electronics for further increasing three-diemsnional electrode pole piece
Conductance.
Preferably, carburizing temperature is 400~600 DEG C in the step (2), carbonization time 3h.It is highly preferred that the step
Suddenly carburizing temperature is 500 DEG C in (2), carbonization time 3h.
The present invention provides a kind of three-diemsnional electrode pole piece, the three-diemsnional electrode pole piece is prepared using method described above
's.
The present invention also provides a kind of energy storage device, the energy storage device includes three-diemsnional electrode pole piece described above.
Preferably, the energy storage device is lithium ion battery or supercapacitor.
The beneficial effects of the present invention are: the present invention provides a kind of the three-diemsnional electrode pole piece based on aqueous binders, sheet
Invention compared with the existing technology have following advantages and effects
(1) electrode plates that the present invention prepares have price low using water-soluble organic macromolecule material as binder
It is honest and clean, from a wealth of sources, the advantages such as environmental-friendly.
(2) electrode plates that the present invention prepares have porous three-dimensional structure, and such three-dimensional structure is conducive to electrolyte
Infiltration, improves the interface compatibility of electrolyte and active material, effectively improves the discharge-rate characteristic of battery.
(3) present invention employs the foam metals of three-dimensional porous structure as electrode current collecting body, is conducive to increase active matter
The contact area of matter and collector improves the electronic conductivity of electrode plates.
(4) active material is rigidly fastened in inside three-dimensional pole piece by three-diemsnional electrode pole piece prepared by the present invention by rolling, such
Structure can the effectively big active material of buffer volumes effects (for example, silicium cathode material, silicon based anode material, oxo transition metal
Compound etc.) the biggish volume change in charge and discharge process, be conducive to the high rate performance for improving battery, extend battery uses the longevity
Life.
(5) present invention passes through conductive polymer poly (3,4- Ethylenedioxy Thiophene), the polyphenyl for adding doping in the slurry
Amine, polypyrrole replace partial solid phase particle conductive agent (conductive carbon powder, acetylene black, graphene and conductive silver as conductive agent material
Powder), the film with high conductivity, which is easily formed, using it is coated on the surface of active material to the conduction of modified electrode material
Property.Meanwhile being conducive to filling of the slurry in the foam-metal current collector body of three-dimensional porous structure.
(6) the configuration of the present invention is simple, preparation process are easy, and process is easy to accomplish.
Detailed description of the invention
Fig. 1 is the three-diemsnional electrode pole piece structure schematic diagram of the present invention based on aqueous binders:
In figure, 1- active material, 2- conductive agent, 3- binder, the three-dimensional porous metal collector of 4-；
Fig. 2 is three-diemsnional electrode pole piece (the Si-PU-Ni foam- of nickel foam and preparation used in the embodiment of the present invention 1
0) scanning electron microscope (SEM) photograph；
Fig. 3 is that the three-diemsnional electrode pole piece (Si-PU-Ni foam-0) prepared in the embodiment of the present invention 1 is used as lithium-ion electric
The chemical property figure of pond cathode pole piece；
Fig. 4 is that the three-diemsnional electrode pole piece (Si-CMC-Ni foam-0) prepared in the embodiment of the present invention 2 is used as lithium ion
The chemical property figure of negative pole piece of battery；
Fig. 5 is that the three-diemsnional electrode pole piece (Si- (C-CTS)-Ni foam-0) prepared in the embodiment of the present invention 3 is used as lithium
The chemical property figure of ion battery cathode pole piece；
Fig. 6 be the embodiment of the present invention 4 in prepare containing without conductive agent three-diemsnional electrode pole piece (Si-Carbon,
Si-PEDOT:PSS, Si-PEDOT:PSS/Carbon) chemical property figure as lithium ion battery negative electrode；
Fig. 7 contains support carbon-coating in silicon-carbon three wherein for what is prepared under calcination temperatures different in the embodiment of the present invention 5
Tie up chemical property figure of the electrode plates as lithium ion battery negative electrode；
Fig. 8 be prepared in the embodiment of the present invention 6 using foam copper as the silicium cathode three-dimensional pole piece of collector as lithium from
The chemical property figure of sub- negative pole piece of battery；
Fig. 9 is to be prepared in the embodiment of the present invention 7 using nickel foam as the graphite cathode containing support carbon-coating of collector
Chemical property figure of the three-dimensional pole piece as lithium ion battery negative electrode.
Specific embodiment
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to the present invention
It is described further.
A kind of embodiment 1: embodiment of the preparation method of the three-diemsnional electrode pole piece of the present invention based on aqueous binders
Using concentration for 3.8wt.% soluble polyurethane (PU) aqueous solution as binder, simple substance silica flour is as negative electrode active
Substance, acetylene black are conductive agent, and the nickel foam of three-dimensional porous structure is that collector prepares silicium cathode three-dimensional pole piece, experimental procedure:
The production of silicium cathode three-dimensional pole piece: above-mentioned negative electrode active material, above-mentioned binder and above-mentioned conductive agent are mixed, obtained
To mixture, wherein the negative electrode active material accounts for 70% on the basis of the total weight of the mixture,
The binder accounts for 10%, and the conductive agent accounts for 20%；It is solvent with water
Gained mixture is tuned into the negative electrode slurry that viscosity is 2000cps, by the foamed nickel current collector of the three-dimensional porous structure of 1.0mm thickness
It is soaked in slurry, the foamed nickel current collector of three-dimensional porous structure is taken out after complete wetting, is dried at 60 DEG C in vacuum drying oven
Electrode slice is done into, is rolled into roll squeezer with a thickness of the electrode slice of 30 μ m-thicks, is sheared later with sheet-punching machine, the silicon is obtained
Cathode three-dimensional pole piece (is denoted as: Si-PU-Ni foam-0).Its structural schematic diagram is as shown in Figure 1.
Above-mentioned negative electrode slurry is coated on the copper foil of 20 μ m-thicks with film applicator, is dried at 60 DEG C in vacuum drying oven
Electrode slice cuts into negative electrode tab electrode (being denoted as: Si-PU-Cu) as a comparison with sheet-punching machine.
The production of battery: being to electrode, using polyethylene film as diaphragm, with 1M LiPF with lithium piece6/ EC:DEC:DMC (v:v:
V=1:1:1 button cell (CR2025)), which is assembled, for electrolyte carries out constant current charge-discharge test, voltage range 0.01-
1.50V, current density 400mA/g.
Test result is as follows: as shown in Fig. 2, used nickel foam has three-dimensional porous structure (Fig. 2 a), utilizing its institute
In manufactured three-diemsnional electrode pole piece, silicon active material is uniformly embedded in nickel foam (Fig. 2 b-d).It can be seen from figure 3 that using PU
For binder, the traditional electrode pole piece prepared using copper foil charge and discharge in the case where current density is the current density of 400mA/g, for the first time
Coulombic efficiency is only 10%, first discharge specific capacity 3972mAh/g, and capacity decays to rapidly after 20 circulations
294mAh/g, capacity only remains 208mAh/g after 100 circulations.The silicium cathode three-dimensional pole piece of preparation, first discharge specific capacity
For 4085mAh/g, coulombic efficiency is increased to 74% for the first time, after 100 times, still keeps the electric discharge specific volume of 794mAh/g
Amount.By comparing as it can be seen that three-diemsnional electrode piece is conducive to the volume expansion for buffering silicon to a certain extent, so as to improve electrochemistry
Cycle performance.
A kind of embodiment 2: embodiment of the preparation method of the three-diemsnional electrode pole piece of the present invention based on aqueous binders
Using concentration for 2wt.% sodium carboxymethylcellulose (CMC) aqueous solution as binder, acetylene black is conductive agent, simple substance
Silicon powder is as negative electrode active material, and the nickel foam of three-dimensional porous structure is that collector prepares silicium cathode three-dimensional pole piece, experimental procedure:
The production of silicium cathode three-dimensional pole piece: above-mentioned negative electrode active material, above-mentioned binder and above-mentioned conductive agent are mixed, obtained
To mixture, wherein the negative electrode active material accounts for 90% on the basis of the total weight of the mixture,
The binder accounts for 1%, and the conductive agent accounts for 9%；It is that solvent will with water
Gained mixture is tuned into the negative electrode slurry that viscosity is 4000cps, and the foamed nickel current collector of the three-dimensional porous structure of 1.0mm thickness is soaked
It steeps in slurry, the foamed nickel current collector of three-dimensional porous structure is taken out after complete wetting, is dried at 60 DEG C in vacuum drying oven
It at electrode slice, is rolled into roll squeezer with a thickness of the electrode slice of 30 μ m-thicks, is sheared later with sheet-punching machine, it is negative to obtain the silicon
Extremely three-dimensional pole piece (being denoted as: Si-CMC-Ni foam-0).
Above-mentioned negative electrode slurry is coated on the copper foil of 20 μ m-thicks with film applicator, is dried at 60 DEG C in vacuum drying oven
Pole piece cuts into negative electrode tab electrode (being denoted as: Si-CMC-Cu) as a comparison with sheet-punching machine.
The production of battery: being to electrode, using polyethylene film as diaphragm, with 1M LiPF with lithium piece6/ EC:DEC:DMC (v:v:
V=1:1:1 button cell (CR2025)), which is assembled, for electrolyte carries out constant current charge-discharge test, voltage range 0.01-
1.50V, current density 200mA/g.
Test result is as follows: the use of CMC being binder, the traditional electrode pole piece prepared using copper foil is in electricity as seen from Figure 4
Charge and discharge under the current density that current density is 200mA/g, coulombic efficiency is 65% for the first time, first discharge specific capacity 3611mAh/
G, capacity decays to rapidly 227mAh/g after 60 circulations, and capacity only remains 35mAh/g after 100 circulations.Preparation
Three-diemsnional electrode pole piece, first discharge specific capacity 3889mAh/g, coulombic efficiency is 61% for the first time, after 100 times, still
Keep the specific discharge capacity of 1229mAh/g.By comparing as it can be seen that three-diemsnional electrode pole piece is conducive to buffer silicon to a certain extent
Volume expansion, so as to improve electrochemistry cycle performance.
A kind of embodiment 3: embodiment of the preparation method of the three-diemsnional electrode pole piece of the present invention based on aqueous binders
Using concentration for the carboxyl chitosan (C-CTS) of 5wt.% aqueous solution as binder, acetylene black is conductive agent, three-dimensional
Silicium cathode three-dimensional pole piece of the nickel foam of porous structure for collector preparation, experimental procedure:
The production of silicium cathode three-dimensional pole piece: above-mentioned negative electrode active material, above-mentioned binder and above-mentioned conductive agent are mixed, obtained
To mixture, wherein the negative electrode active material accounts for 80% on the basis of the total weight of the mixture,
The binder accounts for 5%, and the conductive agent accounts for 15%；It is that solvent will with water
Gained mixture is tuned into the negative electrode slurry that viscosity is 3000cps, and the foamed nickel current collector of the three-dimensional porous structure of 1.0mm thickness is soaked
It steeps in slurry, the foamed nickel current collector of three-dimensional porous structure is taken out after complete wetting, is dried at 60 DEG C in vacuum drying oven
It at electrode slice, is rolled into roll squeezer with a thickness of the electrode slice of 30 μ m-thicks, is sheared later with sheet-punching machine, it is negative to obtain the silicon
Extremely three-dimensional pole piece (being denoted as: Si- (C-CTS)-Ni foam-0).
Above-mentioned negative electrode slurry is coated on the copper foil of 20 μ m-thicks with film applicator, is dried at 60 DEG C in vacuum drying oven
Electrode plates cut into negative electrode tab electrode (being denoted as: Si- (C-CTS)-Cu) as a comparison with sheet-punching machine.
The production of battery: being to electrode, using polyethylene film as diaphragm, with 1M LiPF with lithium piece6/ EC:DEC:DMC (v:v:
V=1:1:1 button cell (CR2025)), which is assembled, for electrolyte carries out constant current charge-discharge test, voltage range 0.01-
1.50V, current density 400mA/g.
Test result is as follows: from figure 5 it can be seen that the use of C-CTS being binder, being existed using traditional electrode pole piece prepared by copper foil
Charge and discharge under the current density that current density is 400mA/g, coulombic efficiency is 67% for the first time, and first discharge specific capacity is
3618mAh/g, capacity only remains 587mAh/g after 100 circulations.The three-diemsnional electrode pole piece of preparation, first discharge specific capacity are
4026mAh/g, coulombic efficiency is 65% for the first time, after 100 times, still keeps the specific discharge capacity of 1466mAh/g.Pass through
Comparison is as it can be seen that three-diemsnional electrode pole piece is conducive to the volume expansion for buffering silicon to a certain extent, so as to improve electrochemistry circulation
Performance.
A kind of embodiment 4: embodiment of the preparation method of the three-diemsnional electrode pole piece of the present invention based on aqueous binders
Using concentration for 3.5wt.% polyurethane (PU) aqueous solution as binder, simple substance silica flour as negative electrode active material,
The second for being 1:1 with acetylene black (Carbon), PEDOT:PSS (U.S. SigamaAldrich company trade product) and mass ratio
For the mixture of acetylene black and PEDOT:PSS respectively as conductive agent, the nickel foam of three-dimensional porous structure is that the silicon of collector preparation is negative
Extremely three-dimensional pole piece, experimental procedure:
The production of silicium cathode three-dimensional pole piece: above-mentioned negative electrode active material, above-mentioned binder and above-mentioned conductive agent are mixed, obtained
To mixture, wherein the negative electrode active material accounts for 70% on the basis of the total weight of the mixture,
The binder accounts for 10%, and the conductive agent accounts for 20%；It is solvent with water
Gained mixture is tuned into the negative electrode slurry that viscosity is 2000cps, by the foamed nickel current collector of the three-dimensional porous structure of 1.0mm thickness
It is soaked in slurry, the foamed nickel current collector of three-dimensional porous structure is taken out after complete wetting, is dried at 60 DEG C in vacuum drying oven
Electrode plates are done into, is rolled into roll squeezer with a thickness of the electrode slice of 30 μ m-thicks, is sheared later with sheet-punching machine, are obtained described
Silicium cathode three-dimensional pole piece is (using the mixture of acetylene black, PEDOT:PSS and acetylene black and PEDOT:PSS as conductive agent
The three-diemsnional electrode pole piece of preparation is denoted as respectively: Si-Carbon, Si-PEDOT:PSS, Si-PEDOT:PSS/Carbon).
The production of battery: with lithium piece be to electrode, using polyethylene film as diaphragm, with 1M LiPF6/EC:DEC:DMC (v:v:
V=1:1:1 button cell (CR2025)), which is assembled, for electrolyte carries out constant current charge-discharge test, voltage range 0.01-
1.50V, current density 400mA/g.
Test result is as follows: as seen from Figure 6, Si-Carbon electrode slice is in the case where current density is the current density of 400mA/g
Charge and discharge, coulombic efficiency is 74%, first discharge specific capacity 4085mAh/g for the first time, and capacity is surplus after 77 circulations
943mAh/g.The charge and discharge in the case where current density is the current density of 400mA/g of Si-PEDOT:PSS electrode plates, coulomb is imitated for the first time
Rate is 71%, first discharge specific capacity 3944mAh/g, and capacity is 1218mAh/g after 77 circulations.Si-PEDOT:
The charge and discharge in the case where current density is the current density of 400mA/g of PSS/Carbon electrode plates, coulombic efficiency is 71% for the first time, first
Secondary specific discharge capacity is 3971mAh/g, and capacity is 1498mAh/g after 77 circulations.Comparison is mixed as it can be seen that adding in the slurry
Miscellaneous conducting polymer replaces partial solid phase particle conductive agent (such as acetylene black) as conductive agent, is easy to using it in active material
Surface formed have high conductivity film cladding to modified electrode pole piece chemical property.
A kind of embodiment 5: embodiment of the preparation method of the three-diemsnional electrode pole piece of the present invention based on aqueous binders
The preparation of silicium cathode three-dimensional pole piece containing support carbon-coating, experimental procedure:
The production of silicium cathode three-dimensional pole piece containing support carbon-coating: the Si-PEDOT:PSS/ that will be prepared into embodiment 4
Carbon three-diemsnional electrode piece, after being cooled to room temperature under argon atmosphere after 400~600 DEG C of calcining 3h, wherein binder
Carbonization forms support carbon-coating, is obtained after being cooled to room temperature containing support carbon-coating in silicon-carbon three-diemsnional electrode pole piece wherein.
The production of battery: being to electrode, using polyethylene film as diaphragm, with 1M LiPF with lithium piece6/ EC:DEC:DMC (v:v:
V=1:1:1 button cell (CR2025)), which is assembled, for electrolyte carries out constant current charge-discharge test, voltage range 0.01-
1.50V, current density 400mA/g.
Test result is as follows: from fig.7, it can be seen that silicon-carbon three-diemsnional electrode pole piece is after calcining, chemical property increases,
The three-diemsnional electrode pole piece charge and discharge in the case where current density is the current density of 400mA/g prepared after 3h are calcined at 400 DEG C, are put for the first time
Electric specific capacity is 4047mAh/g, and capacity is 1525mAh/g, capacity retention ratio 37.9% after 83 circulations.At 500 DEG C
The three-diemsnional electrode pole piece prepared after calcining 3h charge and discharge in the case where current density is the current density of 400mA/g, discharge specific volume for the first time
Amount is 4004mAh/g, and capacity is 2196mAh/g, capacity retention ratio 54.8% after 83 circulations.In 600 DEG C of calcining 3h
The three-diemsnional electrode pole piece prepared afterwards charge and discharge in the case where current density is the current density of 400mA/g, first discharge specific capacity are
4165mAh/g, capacity is 1791mAh/g, capacity retention ratio 43.0% after 83 circulations.By comparing as it can be seen that 500
The silicon-carbon three-diemsnional electrode pole piece that DEG C condition is prepared after being calcined has most excellent chemical property.
A kind of embodiment 6: embodiment of the preparation method of the three-diemsnional electrode pole piece of the present invention based on aqueous binders
Using concentration for 3.8wt.% soluble polyurethane (PU) aqueous solution as binder, simple substance silica flour is as negative electrode active
Substance, the mixture of acetylene black and PEDOT:PSS that mass ratio is 1:1 are conductive agent, and the foam copper of three-dimensional porous structure is collection
Fluid preparation silicium cathode three-dimensional pole piece, experimental procedure:
The production of silicium cathode three-dimensional pole piece: above-mentioned negative electrode active material, above-mentioned binder and above-mentioned conductive agent are mixed, obtained
To mixture, wherein the negative electrode active material accounts for 70% on the basis of the total weight of the mixture,
The binder accounts for 10%, and the conductive agent accounts for 20%；It is solvent with water
Gained mixture is tuned into the negative electrode slurry that viscosity is 2000cps, by the foamed nickel current collector of the three-dimensional porous structure of 1.0mm thickness
It is soaked in slurry, the foamed nickel current collector of three-dimensional porous structure is taken out after complete wetting, is dried at 60 DEG C in vacuum drying oven
Electrode plates are done into, is rolled into roll squeezer with a thickness of the electrode plates of 30 μ m-thicks, is sheared later with sheet-punching machine, institute is obtained
State silicium cathode three-dimensional pole piece (being denoted as: Si-PU-Cu foam).
By the three-diemsnional electrode pole piece of the Si-PU-Cu foam of above-mentioned preparation, in 500 DEG C of calcining 3h under argon atmosphere
Afterwards, wherein binder is carbonized to form support carbon-coating, and the silicon-carbon three-diemsnional electrode pole piece containing support carbon-coating is obtained after being cooled to room temperature
(being denoted as: Si-C-Cu foam).
Above-mentioned slurry is coated on the copper foil of 20 μ m-thicks with film applicator, is dried at 60 DEG C in vacuum drying oven, with punching
Piece machine cuts into negative electrode tab electrode (being denoted as: Si-PU-Cu-2) as a comparison.
The production of battery: being to electrode, using polyethylene film as diaphragm, with 1M LiPF with lithium piece6/ EC:DEC:DMC (v:v:
V=1:1:1 button cell (CR2025)), which is assembled, for electrolyte carries out constant current charge-discharge test, voltage range 0.01-
1.50V, current density 400mA/g.
Test result is as follows: as seen from Figure 8, Si-PU-Cu-2 electrode slice is in the current density that current density is 400mA/g
Lower charge and discharge, first discharge specific capacity 4164mAh/g, capacity decays to rapidly 0mAh/g after 30 circulations.Use bubble
Foam copper is the three-diemsnional electrode pole piece Si-PU-Cu foam of collector preparation, and first discharge specific capacity 3820mAh/g is passing through
After 100 times, the specific discharge capacity of 418mAh/g is still kept.By comparing as it can be seen that three-diemsnional electrode pole piece is conducive in certain journey
The volume expansion of silicon is buffered on degree, so as to improve electrochemistry cycle performance.Three-diemsnional electrode pole piece is after high-temperature calcination is carbonized
The pole piece of the Si-C-Cufoam of preparation, first discharge specific capacity 3045mAh/g are still kept after 100 times
The specific discharge capacity of 2636mAh/g.As it can be seen that after high-temperature calcination, binder is further converted to support carbon-coating filling for comparison
In three-diemsnional electrode pole piece, be conducive to the chemical property for further increasing electrode plates.
A kind of embodiment 7: embodiment of the preparation method of the three-diemsnional electrode pole piece of the present invention based on aqueous binders
Using concentration for 3.8wt.% soluble polyurethane (PU) aqueous solution as binder, graphite is as negative electrode active material
Matter, acetylene black are conductive agent, and the nickel foam of three-dimensional porous structure is that graphite cathode of the collector preparation containing support carbon-coating is three-dimensional
Pole piece, experimental procedure:
Containing support carbon-coating graphite cathode three-dimensional pole piece production: by above-mentioned negative electrode active material, above-mentioned binder and
Above-mentioned conductive agent mixing, obtains mixture, wherein on the basis of the total weight of the mixture, shared by the negative electrode active material
Weight percent is 90%, and the binder accounts for 5%, and the conductive agent accounts for
5%；It is that gained mixture is tuned into the negative electrode slurry that viscosity is 4000cps by solvent with water, by the three-dimensional porous structure of 1.0mm thickness
Foamed nickel current collector be soaked in slurry, after complete wetting take out three-dimensional porous structure foamed nickel current collector, in vacuum dry
Electrode plates are dried at 60 DEG C in case, are rolled into roll squeezer with a thickness of the electrode plates of 30 μ m-thicks, later with punching
The shearing of piece machine, obtains graphite cathode three-dimensional pole piece.By the graphite cathode three-dimensional pole piece of above-mentioned preparation, under argon atmosphere in
After 500 DEG C of calcining 3h, wherein binder is carbonized to form support carbon-coating, and it is negative that the graphite containing support carbon-coating is obtained after being cooled to room temperature
Extremely three-dimensional pole piece.
The production of battery: being to electrode, using polyethylene film as diaphragm, with 1M LiPF with lithium piece6/ EC:DEC:DMC (v:v:
V=1:1:1 button cell (CR2025)) is assembled for electrolyte, and constant current charge-discharge test, voltage model are carried out under 0.2C multiplying power
It encloses for 0.01-3.0V.
Test result is as follows: as seen from Figure 9, have support carbon-coating graphite cathode three-dimensional pole piece current density be 0.2C times
Charge and discharge under rate, first discharge specific capacity 414mAh/g, coulombic efficiency is 88.7% for the first time, and capacity is tieed up after 96 circulations
It holds in 340mAh/g, capacity retention ratio 82%.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (9)
1. a kind of preparation method of the three-diemsnional electrode pole piece based on aqueous binders, which is characterized in that the method includes following
Step:
(1) aqueous binders, conductive agent and active material are mixed, after obtaining mixture, is modulated the mixture with solvent
At slurry, then the foam-metal current collector body of three-dimensional porous structure is soaked in the slurry, after complete wetting described in taking-up
Three-dimensional porous metal collector；
(2) by three-dimensional porous metal collector obtained in step (1) after drying, rolling, slice, the three-dimensional electricity is obtained
Pole pole piece；
Conductive agent is the mixing of conducting polymer and at least one of conductive carbon powder, acetylene black, graphene in the step (1)
Object, the conducting polymer are the conducting polymer for adulterating PSS；
Active material is at least one of silicon powder and silicon substrate composite negative pole material in the step (1)；
It is carbonized under inert gas shielding atmosphere after slice in the step (2), obtains the three-diemsnional electrode piece.
2. the preparation method of three-diemsnional electrode pole piece according to claim 1, which is characterized in that water in the step (1)
Property binder be water-soluble organic macromolecule material aqueous solution.
3. the preparation method of three-diemsnional electrode pole piece according to claim 2, which is characterized in that water in the step (1)
Dissolubility high-molecular organic material is chitosan derivatives, carboxymethyl cellulose, alginate, water-soluble terpene resin, aqueous poly-
At least one of urethane.
4. the preparation method of three-diemsnional electrode pole piece according to claim 1, which is characterized in that three in the step (1)
The foam-metal current collector body for tieing up porous structure is one of foam copper, nickel foam and foamed aluminium.
5. the preparation method of three-diemsnional electrode pole piece according to claim 1, which is characterized in that in the step (1) with
On the basis of the total weight of the mixture, the active material accounts for 70%~90%, the aqueous bonding
Agent accounts for 1%~10%, and the conductive agent accounts for 9%~20%；The step
(1) viscosity of slurry is 1000cps~5000cps in.
6. the preparation method of three-diemsnional electrode pole piece according to claim 1, which is characterized in that carbon in the step (2)
Changing temperature is 400~600 DEG C, carbonization time 3h.
7. a kind of three-diemsnional electrode pole piece using such as any the method preparation of claim 1-6.
8. a kind of energy storage device, which is characterized in that the energy storage device includes three-diemsnional electrode pole piece as claimed in claim 7.
9. energy storage device according to claim 8, which is characterized in that the energy storage device is lithium ion battery or super electricity
Container.
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| CN105428083A (en) * | 2015-12-30 | 2016-03-23 | 益阳市万京源电子有限公司 | Electrode slurry with high conductivity and high mechanical strength |
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| CN108199004A (en) * | 2017-12-25 | 2018-06-22 | 深圳市山木新能源科技股份有限公司 | The manufacturing method and electrode slice of electrode slice |
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