CN104852013A - Preparation method of three-dimensional electrode slice based on aqueous adhesive - Google Patents
Preparation method of three-dimensional electrode slice based on aqueous adhesive Download PDFInfo
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Abstract
The invention provides a three-dimensional electrode slice based on an aqueous adhesive and a preparation method of the three-dimensional electrode slice. The method comprises the following steps: mixing the aqueous adhesive, a conductive agent and an active substance into slurry according to a certain proportion, and coating a three-dimensional porous metal current collector with the slurry; and performing the operation of drying, rolling, slicing or further carbonization and the like to prepare the three-dimensional electrode slice for a lithium ion battery. A water-soluble organic polymer material is adopted as the adhesive, so that the advantages of low price, wide source, environmental friendliness and the like are realized. The prepared three-dimensional electrode slice has a porous three-dimensional structure. Through the three-dimensional structure, infiltration of electrolyte is facilitated; the interface compatibility between the electrolyte and the active substance is improved; and the discharge rate characteristic of the battery is improved effectively. The three-dimensional electrode slice is simple in structure, simple and convenient in preparation process, and easy to implement.
Description
Technical field
The present invention relates to a kind of preparation method of three-diemsnional electrode pole piece, be specifically related to a kind of preparation method of the three-diemsnional electrode pole piece based on aqueous binders.
Background technology
Along with consumer electronics demand grows steadily, hybrid vehicle and pure electric automobile fast development and new energy grid-connected power station project construction paces are accelerated, and high-performance energy-storage battery becomes one of core technology greatly developed.Wherein, lithium ion battery has a high potential in fields such as distributed power generation energy storage because of advantages such as its high voltage, Large Copacity, cycle performance are good, low stain.Along with the continuous lifting of lithium ion battery cost performance, lithium electricity replaces the trend of the conventional batteries such as plumbic acid, Ni-MH battery day by day obvious.The performance of lithium ion battery and the performance of active material and electrode slice structure closely related.At present, common anode material for lithium-ion batteries has cobalt acid lithium, LiFePO4 and ternary material, negative material mainly contains graphite, lithium titanate, silica-base material, transition metal oxide, all there is the problem of electronic conductance rate variance in above-mentioned active material (except graphite cathode) major part, also there is the problem of bulk effect in some material (such as, silica-base material and transition metal material).Therefore, design and develop the bulk effect that also can play certain inhibit activities material while novel electrode chip architecture is beneficial to the electronic conductance improving pole piece and there is certain realistic meaning.
Positive/negative collector conventional in business is aluminium/Copper Foil, and the manufacture craft of pole piece is by containing conductive agent, and the slurry of active material adheres to the surface of Copper Foil by binding agent, after oven dry, roll extrusion obtains electrode plates under a certain pressure.The interfacial property of this electrode affects the charge-discharge performance of electrode slice to a great extent.Meanwhile, because this foil-like collection liquid surface is comparatively smooth, the active material that some bulk effects are larger is easily peeled off from foil-like collector in charge and discharge process.The foam copper of CN 102437313A patent employing three-dimensional porous structure or nickel foam, as electrode current collecting body, use solid phase filling and compressing method to prepare a kind of negative electrode for high-power metal lithium battery.What this method was conducive to powder lithium and electrode current collecting body directly to contact but bonding fastness remains to be further improved.Have bibliographical information that the compound of Graphene and silicon is attached to chemical property three-dimensional foam graphite network being also conducive to improving electrode slice, but for foam copper or nickel foam, the price of foamy graphite net is higher, and ductility is not enough.(Adv.Mater.2013,25,4673–4677)。
Summary of the invention
The object of the invention is to overcome weak point that prior art exists and provide a kind of preparation method of the three-diemsnional electrode pole piece based on aqueous binders, present invention also offers the three-diemsnional electrode pole piece adopting the method to prepare, and uses thereof.
For achieving the above object, the technical scheme taked: a kind of preparation method of the three-diemsnional electrode pole piece based on aqueous binders, said method comprising the steps of:
(1) aqueous binders, conductive agent and active material are mixed, after obtaining mixture, with solvent, described mixture is modulated into slurry, then the foam-metal current collector body of three-dimensional porous structure is soaked in described slurry, after complete wetting, take out described three-dimensional porous metal collector;
(2) the three-dimensional porous metal collector obtained in step (1) is obtained described three-diemsnional electrode pole piece after oven dry, roll extrusion, section.
Preferably, in described step (1), aqueous binders is the aqueous solution of water-soluble organic macromolecule material.
Preferably, in described step (1), water-soluble organic macromolecule material is at least one in chitosan derivatives, carboxymethyl cellulose, alginate, water-soluble terpene resin, aqueous polyurethane.
Preferably, in described step (1), conductive agent is at least one in conducting polymer, conductive carbon powder, acetylene black, Graphene and conductive silver powder; In described step (1), the foam-metal current collector body of three-dimensional porous structure is the one in foam copper, nickel foam and foamed aluminium; In described step (1), active material is at least one in LiFePO4, cobalt acid lithium, LiMn2O4, nickel cobalt manganese, nickel ion doped, LiNiPO, cobalt phosphate lithium, lithium manganese phosphate and rich lithium solid solution cathode material, or described active material is at least one in silica flour, graphite, lithium titanate, metal oxide negative material, tinbase composite negative pole material and silica-based composite negative pole material.Preferably, in described step (1), conducting polymer is at least one in poly-(3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid), polyaniline and polypyrrole.More preferably, conductive agent is the mixture of one or more in conducting polymer and conductive carbon powder, acetylene black, Graphene and conductive silver powder in described step (1).In the present invention when selecting negative material as active material, the three-diemsnional electrode pole piece prepared is three-dimensional negative electricity pole piece; When selecting positive electrode as active material, the three-diemsnional electrode pole piece prepared is three-dimensional anode electrode sheet.
Preferably,, in described step (1) with described mixture total weight amount for benchmark, described active material accounts for 70% ~ 90%, described aqueous binders accounts for 1% ~ 10%, and described conductive agent accounts for 9% ~ 20%; In described step (1), the viscosity of slurry is 1000cps ~ 5000cps.Preferably, described in described step (1), solvent is water.
Preferably, in described step (2), carbonization under inert gas shielding atmosphere after section, obtains described three-diemsnional electrode pole piece.Aqueous binders carbonization is formed and supports carbon-coating in above process, is conducive to the electronic conductance improving three-diemsnional electrode pole piece further.
Preferably, in described step (2), carburizing temperature is 400 ~ 600 DEG C, and carbonization time is 3h.More preferably, in described step (2), carburizing temperature is 500 DEG C, and carbonization time is 3h.
The invention provides a kind of three-diemsnional electrode pole piece, described three-diemsnional electrode pole piece adopts method described above to prepare.
Present invention also offers a kind of energy storage device, described energy storage device comprises three-diemsnional electrode pole piece described above.
Preferably, described energy storage device is lithium ion battery or ultracapacitor.
Beneficial effect of the present invention is: the invention provides a kind of three-diemsnional electrode pole piece based on aqueous binders, the present invention has following advantage and effect relative to prior art:
(1) electrode plates that the present invention prepares adopts water-soluble organic macromolecule material to have the advantages such as cheap, wide material sources, environmental friendliness as binding agent.
(2) electrode plates that the present invention prepares has porous three-dimensional structure, and this kind of 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.
(3) foam metal that present invention employs three-dimensional porous structure, as electrode current collecting body, is conducive to the contact area increasing active material and collector, improves the electronic conductivity of electrode plates.
(4) the three-diemsnional electrode pole piece prepared of the present invention, through roll extrusion, active material is tightly locked in three-dimensional pole piece inside, this kind of structure can active material that effectively buffer volumes effect is large (such as, silicium cathode material, silicon based anode material, transition metal oxide etc.) change in volume larger in charge and discharge process, be conducive to the high rate performance improving battery, extend the useful life of battery.
(5) the present invention is by adding the conductive polymer poly (3 of doping in the slurry, 4-Ethylenedioxy Thiophene), polyaniline, polypyrrole as conductive agent material replace partial solid phase particle conductive agent (conductive carbon powder, acetylene black, Graphene and conductive silver powder), utilize it to be easy to be formed the film with high conductivity and be coated on the surface of active material thus the conductivity of modified electrode material.Meanwhile, the filling of slurry in the foam-metal current collector body of three-dimensional porous structure is conducive to.
(6) structure of the present invention is simple, preparation technology is easy, and process easily realizes.
Accompanying drawing explanation
Fig. 1 is the three-diemsnional electrode pole piece structure schematic diagram based on aqueous binders of the present invention:
In figure, 1-active material, 2-conductive agent, 3-binding agent, the three-dimensional porous metal collector of 4-;
Fig. 2 is the scanning electron microscope (SEM) photograph of the three-diemsnional electrode pole piece (Si-PU-Nifoam-0) of nickel foam and the preparation used in embodiments of the invention 1;
Fig. 3 is the chemical property figure of three-diemsnional electrode pole piece (Si-PU-Ni foam-0) as lithium ion battery negative electrode of preparation in embodiments of the invention 1;
Fig. 4 is the chemical property figure of three-diemsnional electrode pole piece (Si-CMC-Ni foam-0) as lithium ion battery negative electrode of preparation in embodiments of the invention 2;
Fig. 5 is the chemical property figure of three-diemsnional electrode pole piece (Si-(C-CTS)-Ni foam-0) as lithium ion battery negative electrode of preparation in embodiments of the invention 3;
Fig. 6 be in embodiments of the invention 4 preparation containing the three-diemsnional electrode pole piece (Si-Carbon, Si-PEDOT:PSS, Si-PEDOT:PSS/Carbon) without conductive agent as the chemical property figure of lithium ion battery negative electrode;
Fig. 7 supports the chemical property figure of carbon-coating silicon-carbon three-diemsnional electrode pole piece wherein as lithium ion battery negative electrode containing of preparing under different calcining heat in embodiments of the invention 5;
Fig. 8 be in embodiments of the invention 6 preparation take foam copper as the chemical property figure of the three-dimensional pole piece of silicium cathode as lithium ion battery negative electrode of collector;
Fig. 9 be in embodiments of the invention 7 preparation with nickel foam be collector containing the chemical property figure of the three-dimensional pole piece of the graphite cathode supporting carbon-coating as lithium ion battery negative electrode.
Embodiment
For better the object, technical solutions and advantages of the present invention being described, below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1: a kind of embodiment of the preparation method of the three-diemsnional electrode pole piece based on aqueous binders of the present invention
Take concentration as soluble polyurethane (PU) aqueous solution of 3.8wt.% be binding agent, simple substance silica flour is as negative electrode active material, and acetylene black is conductive agent, and the nickel foam of three-dimensional porous structure is that collector prepares the three-dimensional pole piece of silicium cathode, experimental procedure:
The making of the three-dimensional pole piece of silicium cathode: above-mentioned negative electrode active material, above-mentioned binding agent and above-mentioned conductive agent are mixed, obtain mixture, wherein with described mixture total weight amount for benchmark, described negative electrode active material accounts for 70%, described binding agent accounts for 10%, and described conductive agent accounts for 20%; Be solvent with water be the cathode size of 2000cps by gained mixture furnishing viscosity, the nickel foam collector of three-dimensional porous structure thick for 1.0mm is soaked in slurry, the nickel foam collector of three-dimensional porous structure is taken out after complete wetting, at 60 DEG C, electrode slice is dried in vacuum drying oven, being rolled into thickness with roll squeezer is 30 μm of thick electrode slices, shear with sheet-punching machine afterwards, obtain the three-dimensional pole piece (being designated as: Si-PU-Ni foam-0) of described silicium cathode.Its structural representation as shown in Figure 1.
Above-mentioned cathode size film applicator is coated on 20 μm of thick Copper Foils, in vacuum drying oven, at 60 DEG C, is dried into electrode slice, cuts into negative plate electrode (being designated as: Si-PU-Cu) as a comparison with sheet-punching machine.
The making of battery: be to electrode with lithium sheet take polyethylene film as barrier film, with 1M LiPF
6/ EC:DEC:DMC (v:v:v=1:1:1) assembles button cell (CR2025) for electrolyte and carries out constant current charge-discharge test, and voltage range is 0.01-1.50V, and current density is 400mA/g.
Result of the test is as follows: as shown in Figure 2, and the nickel foam used has three-dimensional porous structure, and (Fig. 2 a), utilizes in the three-diemsnional electrode pole piece made by it, and silicon active material is embedded in (Fig. 2 b-d) in nickel foam uniformly.As seen from Figure 3, use PU is binding agent, use traditional electrode pole piece discharge and recharge under the current density of current density for 400mA/g prepared by Copper Foil, coulombic efficiency is only 10% first, first discharge specific capacity is 3972mAh/g, after 20 circulations, capacity decays to 294mAh/g rapidly, capacity only surplus 208mAh/g after 100 circulations.The three-dimensional pole piece of silicium cathode of preparation, first discharge specific capacity is 4085mAh/g, and coulombic efficiency brings up to 74% first, after 100 times, still keeps the specific discharge capacity of 794mAh/g.Visible by contrasting, three-diemsnional electrode sheet is conducive to the volumetric expansion cushioning silicon to a certain extent, thus improves electrochemistry cycle performance.
Embodiment 2: a kind of embodiment of the preparation method of the three-diemsnional electrode pole piece based on aqueous binders of the present invention
Take concentration as sodium carboxymethylcellulose (CMC) aqueous solution of 2wt.% be binding agent, acetylene black is conductive agent, and simple substance silica flour is as negative electrode active material, and the nickel foam of three-dimensional porous structure is that collector prepares the three-dimensional pole piece of silicium cathode, experimental procedure:
The making of the three-dimensional pole piece of silicium cathode: above-mentioned negative electrode active material, above-mentioned binding agent and above-mentioned conductive agent are mixed, obtain mixture, wherein with described mixture total weight amount for benchmark, described negative electrode active material accounts for 90%, described binding agent accounts for 1%, and described conductive agent accounts for 9%; Be solvent with water be the cathode size of 4000cps by gained mixture furnishing viscosity, the nickel foam collector of three-dimensional porous structure thick for 1.0mm is soaked in slurry, the nickel foam collector of three-dimensional porous structure is taken out after complete wetting, at 60 DEG C, electrode slice is dried in vacuum drying oven, being rolled into thickness with roll squeezer is 30 μm of thick electrode slices, shear with sheet-punching machine afterwards, obtain the three-dimensional pole piece (being designated as: Si-CMC-Ni foam-0) of described silicium cathode.
Above-mentioned cathode size film applicator is coated on 20 μm of thick Copper Foils, in vacuum drying oven, at 60 DEG C, is dried into pole piece, cuts into negative plate electrode (being designated as: Si-CMC-Cu) as a comparison with sheet-punching machine.
The making of battery: be to electrode with lithium sheet take polyethylene film as barrier film, with 1M LiPF
6/ EC:DEC:DMC (v:v:v=1:1:1) assembles button cell (CR2025) for electrolyte and carries out constant current charge-discharge test, and voltage range is 0.01-1.50V, and current density is 200mA/g.
Result of the test is as follows: as seen from Figure 4, use CMC is binding agent, use traditional electrode pole piece discharge and recharge under the current density of current density for 200mA/g prepared by Copper Foil, coulombic efficiency is 65% first, first discharge specific capacity is 3611mAh/g, after 60 circulations, capacity decays to 227mAh/g rapidly, capacity only surplus 35mAh/g after 100 circulations.The three-diemsnional electrode pole piece of preparation, first discharge specific capacity is 3889mAh/g, and coulombic efficiency is 61% first, after 100 times, still keeps the specific discharge capacity of 1229mAh/g.Visible by contrasting, three-diemsnional electrode pole piece is conducive to the volumetric expansion cushioning silicon to a certain extent, thus improves electrochemistry cycle performance.
Embodiment 3: a kind of embodiment of the preparation method of the three-diemsnional electrode pole piece based on aqueous binders of the present invention
Take concentration as the aqueous solution of the using carboxyl chitosan (C-CTS) of 5wt.% be binding agent, acetylene black is conductive agent, and the nickel foam of three-dimensional porous structure is the three-dimensional pole piece of silicium cathode prepared by collector, experimental procedure:
The making of the three-dimensional pole piece of silicium cathode: above-mentioned negative electrode active material, above-mentioned binding agent and above-mentioned conductive agent are mixed, obtain mixture, wherein with described mixture total weight amount for benchmark, described negative electrode active material accounts for 80%, described binding agent accounts for 5%, and described conductive agent accounts for 15%; Be solvent with water be the cathode size of 3000cps by gained mixture furnishing viscosity, the nickel foam collector of three-dimensional porous structure thick for 1.0mm is soaked in slurry, the nickel foam collector of three-dimensional porous structure is taken out after complete wetting, at 60 DEG C, electrode slice is dried in vacuum drying oven, being rolled into thickness with roll squeezer is 30 μm of thick electrode slices, shear with sheet-punching machine afterwards, obtain the three-dimensional pole piece (being designated as: Si-(C-CTS)-Ni foam-0) of described silicium cathode.
Above-mentioned cathode size film applicator is coated on 20 μm of thick Copper Foils, in vacuum drying oven, at 60 DEG C, is dried into electrode plates, cuts into negative plate electrode (being designated as: Si-(C-CTS)-Cu) as a comparison with sheet-punching machine.
The making of battery: be to electrode with lithium sheet take polyethylene film as barrier film, with 1M LiPF
6/ EC:DEC:DMC (v:v:v=1:1:1) assembles button cell (CR2025) for electrolyte and carries out constant current charge-discharge test, and voltage range is 0.01-1.50V, and current density is 400mA/g.
Result of the test is as follows: as seen from Figure 5, use C-CTS is binding agent, use traditional electrode pole piece discharge and recharge under the current density of current density for 400mA/g prepared by Copper Foil, coulombic efficiency is 67% first, first discharge specific capacity is 3618mAh/g, capacity only surplus 587mAh/g after 100 circulations.The three-diemsnional electrode pole piece of preparation, first discharge specific capacity is 4026mAh/g, and coulombic efficiency is 65% first, after 100 times, still keeps the specific discharge capacity of 1466mAh/g.Visible by contrasting, three-diemsnional electrode pole piece is conducive to the volumetric expansion cushioning silicon to a certain extent, thus improves electrochemistry cycle performance.
Embodiment 4: a kind of embodiment of the preparation method of the three-diemsnional electrode pole piece based on aqueous binders of the present invention
Take concentration as polyurethane (PU) aqueous solution of 3.5wt.% be binding agent, simple substance silica flour is as negative electrode active material, be that the mixture of the acetylene black of 1:1 and PEDOT:PSS is as conductive agent using acetylene black (Carbon), PEDOT:PSS (U.S. SigamaAldrich company trade product) and mass ratio, the nickel foam of three-dimensional porous structure is the three-dimensional pole piece of silicium cathode prepared by collector, experimental procedure:
The making of the three-dimensional pole piece of silicium cathode: above-mentioned negative electrode active material, above-mentioned binding agent and above-mentioned conductive agent are mixed, obtain mixture, wherein with described mixture total weight amount for benchmark, described negative electrode active material accounts for 70%, described binding agent accounts for 10%, and described conductive agent accounts for 20%, be solvent with water be the cathode size of 2000cps by gained mixture furnishing viscosity, the nickel foam collector of three-dimensional porous structure thick for 1.0mm is soaked in slurry, the nickel foam collector of three-dimensional porous structure is taken out after complete wetting, at 60 DEG C, electrode plates is dried in vacuum drying oven, being rolled into thickness with roll squeezer is 30 μm of thick electrode slices, shear with sheet-punching machine afterwards, obtain the three-dimensional pole piece of described silicium cathode (with acetylene black, the three-diemsnional electrode pole piece that the mixture of PEDOT:PSS and acetylene black and PEDOT:PSS is prepared respectively as conductive agent is designated as respectively: Si-Carbon, Si-PEDOT:PSS, Si-PEDOT:PSS/Carbon).
The making of battery: be to electrode with lithium sheet, take polyethylene film as barrier film, with 1M LiPF6/EC:DEC:DMC (v:v:v=1:1:1) for electrolyte assembling button cell (CR2025) carries out constant current charge-discharge test, voltage range is 0.01-1.50V, and current density is 400mA/g.
Result of the test is as follows: as seen from Figure 6, the discharge and recharge under current density is the current density of 400mA/g of Si-Carbon electrode slice, and coulombic efficiency is 74% first, and first discharge specific capacity is 4085mAh/g, and after 77 circulations, capacity remains 943mAh/g.The discharge and recharge under current density is the current density of 400mA/g of Si-PEDOT:PSS electrode plates, coulombic efficiency is 71% first, and first discharge specific capacity is 3944mAh/g, and after 77 circulations, capacity is 1218mAh/g.The discharge and recharge under current density is the current density of 400mA/g of Si-PEDOT:PSS/Carbon electrode plates, coulombic efficiency is 71% first, and first discharge specific capacity is 3971mAh/g, and after 77 circulations, capacity is 1498mAh/g.Contrast visible, the conducting polymer adding doping in the slurry replaces partial solid phase particle conductive agent (as acetylene black) as conductive agent, utilizes it to be easy to be formed on the surface of active material the coated thus chemical property of modified electrode pole piece of the film with high conductivity.
Embodiment 5: a kind of embodiment of the preparation method of the three-diemsnional electrode pole piece based on aqueous binders of the present invention
Preparation containing the three-dimensional pole piece of the silicium cathode supporting carbon-coating, experimental procedure:
Making containing the three-dimensional pole piece of the silicium cathode supporting carbon-coating: by the Si-PEDOT:PSS/Carbon three-diemsnional electrode sheet be prepared in embodiment 4; after calcining 3h in 400 ~ 600 DEG C after being cooled to room temperature under argon atmosphere; wherein binding agent carbonization is formed and supports carbon-coating, obtains containing supporting carbon-coating silicon-carbon three-diemsnional electrode pole piece wherein after being cooled to room temperature.
The making of battery: be to electrode with lithium sheet take polyethylene film as barrier film, with 1M LiPF
6/ EC:DEC:DMC (v:v:v=1:1:1) assembles button cell (CR2025) for electrolyte and carries out constant current charge-discharge test, and voltage range is 0.01-1.50V, and current density is 400mA/g.
Result of the test is as follows: as seen from Figure 7, silicon-carbon three-diemsnional electrode pole piece is after calcining, chemical property increases, discharge and recharge under the current density that the three-diemsnional electrode pole piece prepared after 400 DEG C of calcining 3h is 400mA/g in current density, first discharge specific capacity is 4047mAh/g, after 83 circulations, capacity is 1525mAh/g, and capability retention is 37.9%.Discharge and recharge under the current density that the three-diemsnional electrode pole piece prepared after 500 DEG C of calcining 3h is 400mA/g in current density, first discharge specific capacity is 4004mAh/g, and after 83 circulations, capacity is 2196mAh/g, and capability retention is 54.8%.Discharge and recharge under the current density that the three-diemsnional electrode pole piece prepared after 600 DEG C of calcining 3h is 400mA/g in current density, first discharge specific capacity is 4165mAh/g, and after 83 circulations, capacity is 1791mAh/g, and capability retention is 43.0%.Visible by contrasting, after 500 DEG C of conditions are calcined, the silicon-carbon three-diemsnional electrode pole piece of preparation has the most excellent chemical property.
Embodiment 6: a kind of embodiment of the preparation method of the three-diemsnional electrode pole piece based on aqueous binders of the present invention
Take concentration as soluble polyurethane (PU) aqueous solution of 3.8wt.% be binding agent, simple substance silica flour is as negative electrode active material, mass ratio is the acetylene black of 1:1 and the mixture of PEDOT:PSS is conductive agent, the foam copper of three-dimensional porous structure is that collector prepares the three-dimensional pole piece of silicium cathode, experimental procedure:
The making of the three-dimensional pole piece of silicium cathode: above-mentioned negative electrode active material, above-mentioned binding agent and above-mentioned conductive agent are mixed, obtain mixture, wherein with described mixture total weight amount for benchmark, described negative electrode active material accounts for 70%, described binding agent accounts for 10%, and described conductive agent accounts for 20%; Be solvent with water be the cathode size of 2000cps by gained mixture furnishing viscosity, the nickel foam collector of three-dimensional porous structure thick for 1.0mm is soaked in slurry, the nickel foam collector of three-dimensional porous structure is taken out after complete wetting, at 60 DEG C, electrode plates is dried in vacuum drying oven, being rolled into thickness with roll squeezer is 30 μm of thick electrode plates, shear with sheet-punching machine afterwards, obtain the three-dimensional pole piece (being designated as: Si-PU-Cu foam) of described silicium cathode.
By the three-diemsnional electrode pole piece of the Si-PU-Cu foam of above-mentioned preparation; under argon atmosphere after 500 DEG C of calcining 3h; wherein binding agent carbonization is formed and supports carbon-coating, obtains the silicon-carbon three-diemsnional electrode pole piece (being designated as: Si-C-Cu foam) containing supporting carbon-coating after being cooled to room temperature.
Above-mentioned slurry film applicator is coated on 20 μm of thick Copper Foils, dries at 60 DEG C in vacuum drying oven, cut into negative plate electrode (being designated as: Si-PU-Cu-2) as a comparison with sheet-punching machine.
The making of battery: be to electrode with lithium sheet take polyethylene film as barrier film, with 1M LiPF
6/ EC:DEC:DMC (v:v:v=1:1:1) assembles button cell (CR2025) for electrolyte and carries out constant current charge-discharge test, and voltage range is 0.01-1.50V, and current density is 400mA/g.
Result of the test is as follows: as seen from Figure 8, the discharge and recharge under current density is the current density of 400mA/g of Si-PU-Cu-2 electrode slice, and first discharge specific capacity is 4164mAh/g, and after 30 circulations, capacity decays to 0mAh/g rapidly.Use the three-diemsnional electrode pole piece Si-PU-Cu foam that foam copper is prepared for collector, first discharge specific capacity is 3820mAh/g, after 100 times, still keeps the specific discharge capacity of 418mAh/g.Visible by contrasting, three-diemsnional electrode pole piece is conducive to the volumetric expansion cushioning silicon to a certain extent, thus improves electrochemistry cycle performance.The pole piece of the Si-C-Cufoam that three-diemsnional electrode pole piece is prepared after high-temperature calcination carbonization, first discharge specific capacity is 3045mAh/g, after 100 times, still keeps the specific discharge capacity of 2636mAh/g.Contrast visible, after high-temperature calcination, binding agent is further converted to support carbon-coating and is filled in three-diemsnional electrode pole piece, is conducive to the chemical property improving electrode plates further.
Embodiment 7: a kind of embodiment of the preparation method of the three-diemsnional electrode pole piece based on aqueous binders of the present invention
Take concentration as soluble polyurethane (PU) aqueous solution of 3.8wt.% be binding agent, graphite is as negative electrode active material, acetylene black is conductive agent, and the nickel foam of three-dimensional porous structure is the three-dimensional pole piece of the graphite cathode of collector preparation containing support carbon-coating, experimental procedure:
Making containing the three-dimensional pole piece of the graphite cathode supporting carbon-coating: above-mentioned negative electrode active material, above-mentioned binding agent and above-mentioned conductive agent are mixed, obtain mixture, wherein with described mixture total weight amount for benchmark, described negative electrode active material accounts for 90%, described binding agent accounts for 5%, and described conductive agent accounts for 5%; Be solvent with water be the cathode size of 4000cps by gained mixture furnishing viscosity, the nickel foam collector of three-dimensional porous structure thick for 1.0mm is soaked in slurry, the nickel foam collector of three-dimensional porous structure is taken out after complete wetting, at 60 DEG C, electrode plates is dried in vacuum drying oven, being rolled into thickness with roll squeezer is 30 μm of thick electrode plates, shear with sheet-punching machine afterwards, obtain the three-dimensional pole piece of graphite cathode.By three-dimensional for the graphite cathode of above-mentioned preparation pole piece, under argon atmosphere after 500 DEG C of calcining 3h, wherein binding agent carbonization is formed and supports carbon-coating, obtains containing the three-dimensional pole piece of the graphite cathode supporting carbon-coating after being cooled to room temperature.
The making of battery: be to electrode with lithium sheet take polyethylene film as barrier film, with 1M LiPF
6/ EC:DEC:DMC (v:v:v=1:1:1) assembles button cell (CR2025) for electrolyte and carry out constant current charge-discharge test under 0.2C multiplying power, and voltage range is 0.01-3.0V.
Result of the test is as follows: as seen from Figure 9, have the three-dimensional pole piece of the graphite cathode discharge and recharge under current density is 0.2C multiplying power supporting carbon-coating, first discharge specific capacity is 414mAh/g, and coulombic efficiency is 88.7% first, after 96 circulations, capacity dimension is held in 340mAh/g, and capability retention is 82%.
Finally to should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention but not limiting the scope of the invention; although be explained in detail the present invention with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify to technical scheme of the present invention or equivalent replacement, and not depart from essence and the scope of technical solution of the present invention.
Claims (10)
1., based on a preparation method for the three-diemsnional electrode pole piece of aqueous binders, it is characterized in that, said method comprising the steps of:
(1) aqueous binders, conductive agent and active material are mixed, after obtaining mixture, with solvent, described mixture is modulated into slurry, then the foam-metal current collector body of three-dimensional porous structure is soaked in described slurry, after complete wetting, take out described three-dimensional porous metal collector;
(2) by the three-dimensional porous metal collector that obtains in step (1) after oven dry, roll extrusion, section, obtain described three-diemsnional electrode pole piece.
2. according to the preparation method of the three-diemsnional electrode pole piece described in claim 1, it is characterized in that, in described step (1), aqueous binders is the aqueous solution of water-soluble organic macromolecule material.
3. according to the preparation method of the three-diemsnional electrode pole piece described in claim 2, it is characterized in that, in described step (1), water-soluble organic macromolecule material is at least one in chitosan derivatives, carboxymethyl cellulose, alginate, water-soluble terpene resin, aqueous polyurethane.
4. according to the preparation method of the three-diemsnional electrode pole piece described in claim 1, it is characterized in that, in described step (1), conductive agent is at least one in conducting polymer, conductive carbon powder, acetylene black, Graphene and conductive silver powder; In described step (1), the foam-metal current collector body of three-dimensional porous structure is the one in foam copper, nickel foam and foamed aluminium; In described step (1), active material is at least one in LiFePO4, cobalt acid lithium, LiMn2O4, nickel cobalt manganese, nickel ion doped, LiNiPO, cobalt phosphate lithium, lithium manganese phosphate and rich lithium solid solution cathode material, or described active material is at least one in silica flour, graphite, lithium titanate, metal oxide negative material, tinbase composite negative pole material and silica-based composite negative pole material.
5. according to the preparation method of the three-diemsnional electrode pole piece described in claim 1, it is characterized in that, in described step (1) with described mixture total weight amount for benchmark, described active material accounts for 70% ~ 90%, described aqueous binders accounts for 1% ~ 10%, and described conductive agent accounts for 9% ~ 20%; In described step (1), the viscosity of slurry is 1000cps ~ 5000cps.
6. according to the preparation method of the three-diemsnional electrode pole piece described in claim 1, it is characterized in that, in described step (2), carbonization under inert gas shielding atmosphere after section, obtains described three-diemsnional electrode sheet.
7. according to the preparation method of the three-diemsnional electrode pole piece described in claim 6, it is characterized in that, in described step (2), carburizing temperature is 400 ~ 600 DEG C, and carbonization time is 3h.
8. one kind adopt as arbitrary in claim 1-7 as described in the three-diemsnional electrode pole piece prepared of method.
9. an energy storage device, is characterized in that, described energy storage device comprises three-diemsnional electrode pole piece as claimed in claim 8.
10. energy storage device according to claim 9, is characterized in that, described energy storage device is lithium ion battery or ultracapacitor.
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