CN104269515A - Negative electrode piece of lithium ion battery, preparation method of negative electrode piece and lithium ion battery - Google Patents
Negative electrode piece of lithium ion battery, preparation method of negative electrode piece and lithium ion battery Download PDFInfo
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Abstract
The invention discloses a negative electrode piece of a lithium ion battery, a preparation method of the negative electrode piece and a lithium ion battery. The preparation method of the negative electrode piece of the lithium ion battery comprises the following steps of (1) preparing a graphene oxide solution with the concentration being 1-20mg/mL; (2) preparing a mixed solution of nano silicon particles and a polymer; (3) fixing a current collector on a receiving device by an electrostatic spraying mode, performing electrostatic spraying on the graphene oxide solution obtained in the step (1) and the mixed solution obtained in the step (2) in sequence to respectively obtain a layer of graphene oxide thin film and a layer of silicon-polymer thin film, and defining the two layers to be layers A and B; (4) repeatedly spraying the graphene oxide solution and the mixed solution to finally form a plurality of AB layer structures on the current collector; and (5) carbonizing the current collector covered with the multiple AB layer structures to obtain the negative electrode piece. According to the preparation method disclosed by the invention, the technology is simple and the cost is relatively low; furthermore, the prepared negative electrode piece is relatively high in capacity and can meet application requirements.
Description
[technical field]
The present invention relates to lithium ion cell electrode sheet, particularly relate to a kind of anode plate for lithium ionic cell and preparation method thereof.
[background technology]
Lithium ion battery has higher energy density because of it and very long useful life is widely used in portable electric appts, as: notebook computer, mobile phone etc.The negative plate of current commercial lithium ion battery mainly adopts graphite material.But the theoretical specific capacity of graphite is only 372mAh/g, in order to improve energy density and the power density of the negative pole of lithium ion battery further, the negative material of development of new is most important.Because the theoretical capacity of silicon is up to 4200mAh/g, simultaneously at occurring in nature rich reserves, therefore have the solution be applied to by silicon materials in lithium ion battery negative.General resolving ideas is, first silicon materials and material with carbon element are mixed with and obtain Si-C composite material, then Si-C composite material is mixed with acetylene black (conductive agent), Kynoar (binding agent) and be made into slurry, even spread to copper foil current collector obtains negative plate.The thinking of current research and development focuses mostly in Si-C composite material preparation process, obtain the Si-C composite material of some special microstructures, if publication number is the Si-C composite material in CN103311523A with nanometer micropore gap, publication number is silicon materials and the rear obtained silicon-graphene oxide film of material with carbon element mixing in CN103050672A.Mix with acetylene black (conductive agent), Kynoar (binding agent) again after preparing Si-C composite material and be made into slurry, be applied on Copper Foil and make negative plate.This process silicon application being made negative plate, technical process is loaded down with trivial details, is not suitable for applying in actual industrial production.
[summary of the invention]
Technical problem to be solved by this invention is: make up above-mentioned the deficiencies in the prior art, propose a kind of anode plate for lithium ionic cell and preparation method thereof, lithium ion battery, preparation method's simple process, cost is lower, and the volumetric properties of obtained negative plate is better, can meet application demand.
Technical problem of the present invention is solved by following technical scheme:
A preparation method for anode plate for lithium ionic cell, comprises the following steps: 1) compound concentration is the graphene oxide solution of 1 ~ 20mg/mL; 2) mixed solution of preparation of nano silicon grain and polymer; Silicon nanoparticle and polymer are dissolved in obtained described mixed solution in alcohol solution, and in described mixed solution, the concentration of described polymer is 1 ~ 50mg/mL, and the mass ratio of described silicon nanoparticle and described polymer is 0.05 ~ 1, and the diameter of described silicon nanoparticle is at 30 ~ 150nm; 3) mode of electrostatic spraying is adopted, collector is fixed on the reception device, step 1 described in electrostatic spraying successively) obtained graphene oxide solution, described step 2) obtained mixed solution, obtain one deck graphene oxide film and one deck silicon-thin polymer film respectively, be defined as AB layer; And through spraying, the mass ratio of described graphene oxide film and described silicon-thin polymer film is 1:6 ~ 1:9; 4) repeat to spray described graphene oxide solution and described mixed solution, finally form multiple AB Rotating fields on a current collector; 5) collector being coated with multiple AB Rotating fields is carried out charing process, obtained negative plate
The anode plate for lithium ionic cell that a kind of basis preparation method as above obtains.
A kind of lithium ion battery, the negative plate of described lithium ion battery is negative plate as above.
The beneficial effect that the present invention is compared with the prior art is:
Anode plate for lithium ionic cell of the present invention and preparation method thereof, adopts the mode of electrostatic spraying by graphene oxide solution direct spraying on collector, formation graphene oxide film layer, A layer; Then the mixed solution of nano silicon material and polymer is sprayed on graphene oxide film layer by electrostatic spraying, form silicon-polymer film layer, B layer, through repeatedly repeating spraying, after forming multiple AB Rotating fields on a current collector, collector is carbonized process together with multiple AB Rotating fields that it covers, directly obtained negative plate.Whole preparation process does not need slurrying coating process in traditional preparation process, simple process, and the use that conductive agent and binding agent can be saved, cost is lower.In obtained negative plate, porous amorphous carbon (polymer carbonization is formationed) reserves cushion space in the volumetric expansion of embedding lithium process for silicon, and the electron transport ability of guarantee material monolithic, guarantees the volumetric properties of negative plate.And A Rotating fields and B Rotating fields stacked in multi-layers, the volumetric expansion stress equilibrium dispersion that can make silicon in layers, guarantees that the physical structure of negative plate is stablized.Experimentally record, the reversible specific capacity first of obtained negative plate is at 960 ~ 1680mAh/g, and after circulation 100 circle, charge specific capacity (de-lithium) is 580 ~ 1008mAh/g, and capability retention is 57.6% ~ 74.5%, better performances, can meet commercial Application requirement.
[accompanying drawing explanation]
Fig. 1 is preparation method's flow chart of the anode plate for lithium ionic cell of the specific embodiment of the invention;
Fig. 2 is the microstructure schematic diagram of the active material on the negative plate of the specific embodiment of the invention;
Fig. 3 is the SEM photo of negative plate obtained in experimental example 3 in the specific embodiment of the invention.
[embodiment]
Contrast accompanying drawing below in conjunction with embodiment the present invention is described in further details.
In order to be applied in battery cathode sheet by silicon materials, general thinking has silicon materials nanometer is changed into zero dimension, a peacekeeping two-dimensional material, i.e. nano silicon particles, nano wire, nanotube and nano thin-film.Then silicon materials and material with carbon element are prepared the special silico-carbo composite material of structure by various technology controlling and process, then Si-C composite material is applied to obtained negative plate on collector by the technique that slurrying is coated with.And the present invention prepares negative plate again after first preparing Si-C composite material, but prepare graphene oxide solution respectively, silicon materials solution, directly formed graphene film, the silicon-thin polymer film of multilayer laminated arrangement by electrostatic coating on a current collector, after charing process, directly obtain negative plate.Whole preparation process changes conventional thinking, and simple process, cost is lower, and the volumetric properties of obtained negative plate is better, can meet application demand.
As shown in Figure 1, be the flow chart of the preparation method of the anode plate for lithium ionic cell of this embodiment, preparation process comprises the following steps:
S1) compound concentration is the graphene oxide solution of 1 ~ 20mg/mL.
Particularly, can adopt and improve Hummer's legal system for graphite oxide, then the graphite oxide of certain mass is accurately taken, be dissolved in the deionized water of certain mass, ultrasonic disperse process, obtains the graphene oxide homogeneous phase aqueous solution of certain mass mark, then by its with absolute ethyl alcohol by volume 1:1 mix, final obtained concentration is the homogeneous phase solution of the graphene oxide of 1 ~ 20mg/mL, is designated as solution M.
S2) mixed solution of preparation of nano silicon grain and polymer; Silicon nanoparticle and polymer are dissolved in obtained described mixed solution in alcohol solution, and the concentration of described polymer is 1 ~ 50mg/mL, the mass ratio of described silicon nanoparticle and described polymer is 0.05 ~ 1, and the diameter of described silicon nanoparticle is at 30 ~ 150nm.
Particularly, weigh a certain amount of silicon nanoparticle and polymer, polymer can be sucrose, soluble starch, citric acid, polyvinyl alcohol, polyvinylpyrrolidone, polyaniline, polypyrrole etc. can carbonize into one or more kinds of mixing in arbitrary polymer of material with carbon element.By silicon nanoparticle and dissolution of polymer in alcohol solution, fully stir, ultrasonic disperse, obtain the mixed solution of silicon nanoparticle and polymer, be designated as solution N.
Preferably, when preparing mixed solution, in alcohol solution, add electric conducting material, such as acetylene black, and the mass ratio of electric conducting material and silicon nanoparticle is 0.2 ~ 5.When not adding electric conducting material, form porous amorphous carbon matrix after polymer charing, energy auxiliary silicon materials conductive, guarantees the conductivity of active material in negative plate.When after interpolation electric conducting material, then significantly can promote the conductivity of silicon materials, and then promote the electric property of obtained negative plate.
Further preferably, when preparing mixed solution, add CNT (carbon nano-tube) or carbon nano-fiber in alcohol solution, the mass ratio of CNT (carbon nano-tube) or carbon nano-fiber and described silicon nanoparticle is 0.2 ~ 5.The CNT (carbon nano-tube) of adding or carbon nano-fiber can play skeletal support effect, stablize silicon-porous charcoal Rotating fields that follow-up charing is formed, promote the mechanical property of this layer.The interpolation of CNT (carbon nano-tube) or carbon nano-fiber simultaneously, contributes on the one hand forming good conductive network, can promote the mechanical property of active material on the other hand, and then promote the chemical property of obtained negative plate.
It should be noted that, the electric conducting material added, and the quality control of CNT (carbon nano-tube) or carbon nano-fiber, being through test of many times to determine to obtain, when controlling in above-mentioned scope, coordinating the concentration of aforementioned M solution, the content of each component in N solution, Comprehensive Control just can guarantee that the mass fraction of final silicon materials in active material layer is a suitable scope, and the high theoretical capacity of silicon materials could be brought into play preferably, guarantees that the volumetric properties of negative plate is better.
S3) mode of electrostatic spraying is adopted, by fixing on the reception device for collector (such as conventional Copper Foil), step S1 described in electrostatic spraying successively) obtained graphene oxide solution, described step S2) obtained mixed solution, obtain one deck graphene oxide film respectively, be defined as A layer and one deck silicon-thin polymer film, be defined as B layer, thus on Copper Foil, form AB Rotating fields; And through spraying, the mass ratio of A layer film and B layer film is 1:6-1:9.
Particularly, copper foil current collector fixed by the receiving system of electrostatic spraying apparatus, by step S1) the solution M that configures loads in syringe, sprayed by solution with certain flow, electrostatic spray under the high voltage electric field of 10 ~ 30kV, spinning head is 5 ~ 15cm to the distance of receiver, ambient temperature is 25 DEG C, air humidity is 40%, spraying certain time length, guarantees that spraying solution forms the quality that film can reach needs.The droplet that spraying is formed obtains one deck graphene oxide film after desolvation on the receiver being coated with Copper Foil, is A layer film.Then by step S2) the solution N that configures loads in syringe, with certain flow, solution is sprayed, electrostatic spray under the high voltage electric field of 10 ~ 30kV, spinning head is 5 ~ 15cm to the distance of receiver, ambient temperature is 25 DEG C, air humidity is 40%, spraying certain time length, guarantees that spraying solution forms the quality that film can reach needs.The droplet that spraying is formed obtains one deck silicon-thin polymer film on A layer film after desolvation, namely on A layer film, define B layer film.
It should be noted that, in above-mentioned M solution and N solution, parameter is determined in above-mentioned scope, the control of quantity for spray during spraying, not arbitrarily for it, but comprehensively determine to obtain through many experiments, the concentration (1 ~ 20mg/mL) of above-mentioned graphene oxide, the concentration (1 ~ 50mg/mL) of polymer, the mass ratio (0.05 ~ 1) of silicon nanoparticle and polymer, the several parameter joint effect of mass ratio (1:6 ~ 1:9) of A layer film and B layer film during spraying, make the mass fraction of silicon materials in active material layer in final obtained negative plate a suitable scope, thus the high theoretical capacity of silicon materials can be brought into play preferably, guarantee that the volumetric properties of negative plate is better.
S4) repeat to spray described graphene oxide solution and described mixed solution, finally form multiple AB Rotating fields on a current collector.In this step, repeat spraying and form sandwich construction, thus the volumetric expansion stress equilibrium dispersion of silicon under highly embedding lithium state can be made in layers, guarantee that the unitary physical structure of negative plate is stablized.It should be noted that, be the Graphene comprising certain mass or the silicon-porous carbon material of obtained certain mass, preferably arrange single layer structure thinner, the more mode of the number of plies obtains certain mass.This mode, and mode that the number of plies less thicker relative to single layer structure, in negative plate, the swelling stress of silicon materials is dispersed in comparatively in sandwich construction, and disperse more open, the stability of structure is better.
Preferably, in step S4) after, entering step S5) carbonize heat treatment before, also comprise step S4 ') (meaning not shown in the figures), adopt the mode of electrostatic spraying, at described step S4) step 1 described in electrostatic spraying on multiple AB Rotating fields of obtaining) obtained graphene oxide solution, form one deck graphene oxide film.One deck graphene oxide film is formed by covering again on B layer film (silicon-thin polymer film) surface; like this; when negative plate is used in battery; the graphene oxide film of negative plate most surface can be protected the silicon materials of below; the silicon materials of protection below, not by the impact of electrolyte, guarantee that the useful life of negative plate is longer.
S5) collector being coated with multiple AB Rotating fields is carried out charing process, obtained negative plate.
Particularly, during charing process, carry out in high temperature carbonization furnace, in an inert atmosphere, with the programming rate of 1 ~ 20 DEG C/min from room temperature to 500 ~ 1000 DEG C, constant temperature 1 ~ 3h, after being then cooled to room temperature, taking out and obtains described negative plate.General collector, such as Copper Foil, its fusing point is higher, therefore can tolerate above-mentioned charing high-temperature process completely, finally obtained negative plate.As shown in Figure 2, be the microstructure schematic diagram of the active material layer on negative plate.Active material comprises A Rotating fields (rGO that graphene oxide film charing is formed) and the B Rotating fields (silicon-porous carbon that silicon-thin polymer film charing is formed) of stacked arrangement, wherein B Rotating fields comprises the porous carbon materials B02 that polymer charing is formed, porous carbon materials parcel silicon materials B01.
Also provide a kind of lithium ion battery in this embodiment, its negative plate is the negative plate obtained according to preparation method described above.
In the preparation method of the negative plate of this embodiment, whole preparation process is no longer first prepare Si-C composite material, and then by Si-C composite material and conductive agent, be coated with after binding agent slurrying, but after directly preparing solution, carbonize process after electrostatic spray and obtain negative plate, whole process is easy to be controlled, and without the need to using conductive agent and binding agent, cost is lower.Obtained negative plate, volumetric properties is better, and reversible specific capacity is at 960 ~ 1680mAh/g first, and after circulation 100 circle, charge specific capacity (de-lithium) is 580 ~ 1008mAh/g, and capability retention, 59.8% ~ 74.5%, can meet commercial Application requirement.
Following by arranging concrete experimental example, the volumetric properties of the negative plate of checking preparation.
Experimental example 1:
The first step: the preparation of graphene oxide homogeneous solution.Adopt and improve Hummer ' s legal system for graphite oxide.Accurately take 160mg graphene oxide, be dissolved in the deionized water of 80mL, ultrasonic, obtain the graphene oxide homogeneous phase solution of 2mg/mL, again by its with absolute ethyl alcohol by volume 1:1 mix, obtain the homogeneous phase solution of the graphene oxide of 1mg/mL, be designated as solution M.
Second step: the preparation of the mixed solution of silicon nanoparticle and polymer.The PVP of precise 40mg silicon nanoparticle (selecting diameter in this experimental example at the silicon nanoparticle of 30 ~ 100nm), 200mg is dissolved in the alcohol solution of 20mL, abundant stirring 4h, ultrasonic 1h, obtains the mixed solution of silicon nanoparticle and polymer, is designated as solution N1.Also be that in N1 solution, the concentration of polymer is 10mg/mL, and the mass ratio of silicon nanoparticle and polymer is 0.2.
3rd step: electrostatic spray solution M.Solution M obtained for the first step is loaded in syringe, electrostatic spray under the high voltage electric field of 25kV, spinning head (receiver is fixed with copper foil current collector to receiver,) distance be 5cm, ambient temperature is 25 DEG C, air humidity is 40%, and the droplet that spraying is formed obtains film A at the upper desolvation of the receiver being coated with Copper Foil.
4th step: electrostatic spray solution N1.Loaded in syringe by solution N1 obtained for second step, electrostatic spray under the high voltage electric field of 25kV, spinning head is 5cm to the distance of receiver, and ambient temperature is 25 DEG C, and air humidity is 40%, and original film A forms film B1.
Wherein in the 3rd step and the 4th step, the flow of spraying and spray time control, and make the mass ratio of final film A and film B1 be 1:6.
5th step: repeat the 3rd step and the 4th step, until form 10 AB1 laminated construction.
6th step: again through electrostatic spray thin film A on the multi-layer film structure that the 5th step obtains, controling parameters during electrostatic spray is identical with the 3rd step.
7th step: the Copper Foil being coated with multi-layer film structure that the 6th step obtains is heat-treated.The film with 10 AB1 laminated construction overlayed on Copper Foil is carried out carbonization treatment.Under high-purity argon gas (purity >99.999%) protection; 600 DEG C are progressively warming up to from room temperature with the programming rate of 5 DEG C/min; and constant temperature 2h, take out sample after being cooled to room temperature, directly obtain the silicium cathode electrode material of stacked in multi-layers.In this experimental example, on final collector, active material load capacity is about 0.3mg/cm
2.
8th step: electrochemical property test.The membrane electrode that 7th step obtains directly is washed into the electrode slice that diameter is 15mm, and using metal lithium sheet as to electrode, microporous polypropylene membrane (Celgard2400) makes barrier film, and electrolyte is 1mol/LLiPF
6solution, solvent is ethylene carbonate (EC)+diethyl carbonate (DEC)+methyl ethyl carbonate (EMC)+vinylene carbonate (VC) solution, the volume ratio of EC:DEC:EMC is 1:1:1, VC mass fraction is in the electrolytic solution 2%.2032 type button cells are assembled in the glove box being full of high-purity argon gas.Utilize Land battery test system at room temperature to carry out constant current charge-discharge performance test to above-mentioned half-cell, current density is 200mA/g, and charging/discharging voltage scope is 0.01 ~ 1.0V.
The maximum reversible specific capacity of the negative plate obtained by above-mentioned steps is 1505mAh/g, and the charge specific capacity (de-lithium) after circulation 100 circle is 900mAh/g, and capability retention is 59.8%.
Experimental example 2: this experimental example is relative to experimental example 1, and difference is only: in the 3rd step and the 4th step, the flow of spraying and spray time control, and make the mass ratio of final film A and film B1 be 1:7.5.Finally, the maximum reversible specific capacity of obtained negative plate is 1580mAh/g, and the charge specific capacity (de-lithium) after circulation 100 circle is 910mAh/g, and capability retention is 57.6%.
Example 1 and experimental example 2 is more known by experiment, and when the mass ratio of film A and film B1 adjusts to some extent, but the volumetric properties of final obtained negative plate is similar.Change to some extent although possible cause is thin film coated mass ratio, but because after polymer P VP carbonization, surplus is less, the mass fraction of silicon materials in active material layer almost quite (between 55-60%), thus causes the performance performance of silicon materials capacity almost identical.
Experimental example 3: this experimental example is relative to experimental example 2, and difference is only: when second step prepares mixed solution, adds acetylene black material and nano carbon tube material.
The first step: identical with the first step in experimental example 1, obtains the homogeneous phase solution of the graphene oxide of 1mg/mL, is designated as solution M.
Second step: the preparation of the mixed solution of silicon nanoparticle and polymer.PVP, 20mg multi-walled carbon nano-tubes and the 40mg acetylene black of precise 40mg silicon nanoparticle (diameter is about 30-100nm), 200mg are dissolved in the alcohol solution of 20mL, abundant stirring 4h, ultrasonic 1h, obtains the polymer homogeneous phase solution of silicon nanoparticle, is designated as solution N2.Also be that in N2 solution, the concentration of polymer is 10mg/mL, and the mass ratio of silicon nanoparticle and polymer is 0.2, and the mass ratio of electric conducting material and silicon nanoparticle is 1, and the mass ratio of CNT (carbon nano-tube) and silicon nanoparticle is 0.5.
3rd step: electrostatic spray solution M, spraying process is identical with the 3rd step in experimental example 1, obtains film A.
4th step: electrostatic spray solution N2, spraying process is identical with the 4th step in experimental example 1, and film A is formed film B2.
In 3rd step and the 4th step, controlled by the flow of spraying and spray time, make the mass ratio of final film A and film B2 be 1:7.5.
5th step: repeat the 3rd step and the 4th step, until form 10 AB2 laminated construction.
6th step: again through electrostatic spray thin film A on the multi-layer film structure that the 5th step obtains, controling parameters during electrostatic spray is identical with the 3rd step.
7th step: the Copper Foil being coated with multi-layer film structure that the 6th step obtains is heat-treated.Heat-treat condition is identical with the 7th step in experimental example 1.
8th step: electrochemical property test.Test condition is identical with the 8th step in experimental example 1.
The maximum reversible specific capacity of the negative plate obtained by above-mentioned steps is 1020mAh/g, and the charge specific capacity (de-lithium) after circulation 100 circle is 760mAh/g, and capability retention is 74.5%.As shown in Figure 3, wherein Fig. 3 a is the photo of negative plate upper surface to the SEM photo of this negative plate, and Fig. 3 b is the photo of negative plate longitudinal cross-section.Can find out that there is obvious stepped construction from Fig. 3 b.
Example 3 and experimental example 2 is more known by experiment, increases acetylene black material and nano carbon tube material preparing when second step prepares mixed solution, can promote the volumetric properties of obtained negative plate.Although increase acetylene black, after nano carbon tube material, cause the mass fraction of silicon materials in active material layer in final obtained negative plate to reduce (about 30%), maximum reversible specific capacity decreases.But the interpolation of above-mentioned material makes on negative plate collector in active material, CNT (carbon nano-tube), acetylene black are that silicon materials construct stable conductive network, thus cyclical stability is promoted.And the interpolation of CNT (carbon nano-tube) makes the structural stability of active material be improved, finally improve the circulation volume performance of negative plate from conductive network and structural stability two aspect.
Experimental example 4: this experimental example is relative to experimental example 3, difference is only: the content of silicon nanoparticle in the mixed solution configured in second step, and the 3rd in step and the 4th step, the flow of spraying and spray time control, and make the change of the mass ratio of final film A and film B1.
The first step: identical with the first step in experimental example 3, obtains the homogeneous phase solution of the graphene oxide of 1mg/mL, is designated as solution M.
Second step: the preparation of the mixed solution of silicon nanoparticle and polymer.PVP, 20mg multi-walled carbon nano-tubes and the 40mg acetylene black of precise 100mg silicon nanoparticle (diameter is about 30-100nm), 200mg are dissolved in the alcohol solution of 20mL, abundant stirring 4h, ultrasonic 1h, obtains the polymer homogeneous phase solution of silicon nanoparticle, is designated as solution N3.Also be that in N3 solution, the concentration of polymer is 10mg/mL, and the mass ratio of silicon nanoparticle and polymer is 0.5, and the mass ratio of electric conducting material and silicon nanoparticle is 0.4, and the mass ratio of CNT (carbon nano-tube) and silicon nanoparticle is 0.2.
3rd step: electrostatic spray solution M, spraying process is identical with the 3rd step in experimental example 1, obtains film A.
4th step: electrostatic spray solution N3, spraying process is identical with the 4th step in experimental example 1, and film A is formed film B3.
In 3rd step and the 4th step, controlled by the flow of spraying and spray time, make the mass ratio of final film A and film B2 be 1:9.
5th step: repeat the 3rd step and the 4th step, until form 10 AB3 laminated construction.
6th step is to the 8th step: identical to the 8th step with the 6th step in experimental example 3.
The maximum reversible specific capacity of the negative plate obtained by above-mentioned steps is 1680mAh/g, and the charge specific capacity (de-lithium) after circulation 100 circle is 1008mAh/g, and capability retention is 60%.
Example 4 and experimental example 3 is more known by experiment, prepare the content that mixed solution heightens silicon nanoparticle preparing second step, and the relative amount (also improving the content of silicon materials relative to Graphene) of B film is improved when electrostatic spray, can promote the maximum reversible specific capacity performance of obtained negative plate, but after circulation, capacity retention correspondingly can decline to some extent.Visible, the content increasing silicon materials might not cause the lifting of capability retention.
Experimental example 5: this experimental example is relative to experimental example 3, and difference is only: in the 3rd step and the 4th step, unit are coating quality change and repeat the number of plies change of lamination during spraying.
The first step: identical with the first step in experimental example 3, obtains the homogeneous phase solution of the graphene oxide of 1mg/mL, is designated as solution M.
Second step: identical with the second step in experimental example 3, obtains the polymer homogeneous phase solution of silicon nanoparticle, is designated as solution N2.
3rd step: electrostatic spray solution M, spraying process is identical with the 3rd step in experimental example 3, and just during spraying, the coating quality of unit are is 3 times of the 3rd step in experimental example 3, thus obtains film A.
4th step: electrostatic spray solution N2, spraying process is identical with the 4th step in experimental example 3, and just during spraying, the coating quality of unit are is 3 times of the 4th step in experimental example 3.
In 3rd step and the 4th step, controlled by the flow of spraying and spray time, still make the mass ratio of final film A and film B2 be 1:7.5.
5th step: repeat the 3rd step and the 4th step, until form 3 AB3 laminated construction.
6th step: the film obtained in the 5th step is again through the 3rd step spraying thin film A, and state modulator is identical with the 3rd step.
7th step is to the 8th step: identical to the 8th step with the 7th step in experimental example 3.
The maximum reversible specific capacity of the negative plate obtained by above-mentioned steps is 1100mAh/g, and the charge specific capacity (de-lithium) after circulation 100 circle is 660mAh/g, and capability retention is 60%.
Example 5 and experimental example 3 is more known by experiment, the obtained quality that is roughly the same, the active material of same composition content, in experimental example 3 stacked point 10 layers, every layer of coating quality is less, the scheme of thinner thickness, than in experimental example 5 stacked point 3 layers, the scheme that every layer thickness is thicker, the conservation rate better performances of capacity, the former is 74.5%, and the latter is only 60%.Show that in the preparation, the number of plies is more, it is less that every layer of thinner scheme is better than the number of plies, every layer of thicker scheme.
Experimental example 6: this experimental example is relative to experimental example 3, and difference is only: in the 5th step, repeats the number of plies change of lamination, increases to 50 AB2 laminated construction.Finally, the maximum reversible specific capacity of obtained negative plate is 965mAh/g, and the charge specific capacity (de-lithium) after circulation 100 circle is 580mAh/g, and capability retention is 60.1%.
Example 6 and experimental example 3 is more known by experiment, and the scheme that the lamination number of plies is set to 10 or 50 is all feasible.But increase the lamination number of plies, increase the content of active material, unit mass specific capacity performance there is no obvious increase, also declines to some extent on the contrary.Reason is: if mass percent one timing of silicon in active material layer, when coating thickness strengthens, the capacity away from the active material of collector plays degradation, so the volumetric properties of unit mass ratio there is no obvious increase.
Reference example: get 80mg silicon nanoparticle, be that 2:2:1:2:10 mix with graphene oxide, CNT (carbon nano-tube), acetylene black and PVP according to mass ratio by silicon nanoparticle (diameter is 30 ~ 100nm), also be graphene oxide quality: (silicon nanoparticle+CNT (carbon nano-tube)+acetylene black+PVP) quality is 1:7.5 (identical with experimental example 3), by the obtained Si-C composite material of homogeneous mixture charing process be mixed to get.By Si-C composite material and acetylene black, Kynoar in mass ratio for 8:1:1 makes slurry.Slurry is uniformly coated on obtained negative plate in copper foil current collector.Test the chemical property of this negative plate, test condition is identical with the 8th step in experimental example 3.The maximum reversible specific capacity recording negative plate is 980mAh/g, and the charge specific capacity (de-lithium) after circulation 100 circle is 368mAh/g, and capability retention is 37.56%.
Compared with reference example by experimental example 1 ~ 6, the volumetric properties of the negative plate that known experimental example 1 ~ 6 is obtained is all better than the volumetric properties of negative plate conventionally obtained in comparative example.Visible, although material relative composition controls the same, pass through electrostatic Spraying technique, and the compound prepared has the structure of stacked in multi-layers, thus be conducive to electricity and the structural stability of holding electrode, the volumetric properties of the negative plate made is better than the negative plate of simple mixing carbonization treatment, and the negative plate volumetric properties prepared according to the process of experimental example 1 ~ 6 is all better, and conservation rate is 57.6% ~ 74.5%.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, make some substituting or obvious modification without departing from the inventive concept of the premise, and performance or purposes identical, all should be considered as belonging to protection scope of the present invention.
Claims (9)
1. a preparation method for anode plate for lithium ionic cell, is characterized in that: comprise the following steps: 1) compound concentration is the graphene oxide solution of 1 ~ 20mg/mL; 2) mixed solution of preparation of nano silicon grain and polymer; Silicon nanoparticle and polymer are dissolved in obtained described mixed solution in alcohol solution, and in described mixed solution, the concentration of described polymer is 1 ~ 50mg/mL, and the mass ratio of described silicon nanoparticle and described polymer is 0.05 ~ 1, and the diameter of described silicon nanoparticle is at 30 ~ 150nm; 3) mode of electrostatic spraying is adopted, collector is fixed on the reception device, step 1 described in electrostatic spraying successively) obtained graphene oxide solution, described step 2) obtained mixed solution, obtain one deck graphene oxide film and one deck silicon-thin polymer film respectively, be defined as AB layer; And through spraying, the mass ratio of described graphene oxide film and described silicon-thin polymer film is 1:6 ~ 1:9; 4) repeat to spray described graphene oxide solution and described mixed solution, finally form multiple AB Rotating fields on a current collector; 5) collector being coated with multiple AB Rotating fields is carried out charing process, obtained negative plate.
2. the preparation method of anode plate for lithium ionic cell according to claim 1, it is characterized in that: described step 2) in, also be included in described alcohol solution and add electric conducting material and obtain described mixed solution, the mass ratio of described electric conducting material and described silicon nanoparticle is 0.2 ~ 5.
3. the preparation method of anode plate for lithium ionic cell according to claim 1 and 2, it is characterized in that: described step 2) in, also be included in described alcohol solution and add CNT (carbon nano-tube) or carbon nano-fiber obtains described mixed solution, the mass ratio of described CNT (carbon nano-tube) or described carbon nano-fiber and described silicon nanoparticle is 0.2 ~ 5.
4. the preparation method of anode plate for lithium ionic cell according to claim 1, it is characterized in that: described step 4) and described step 5) between also comprise step 4 '): adopt the mode of electrostatic spraying, in described step 4) step 1 described in electrostatic spraying on multiple AB Rotating fields of obtaining) obtained graphene oxide solution, form one deck graphene oxide film.
5. the preparation method of anode plate for lithium ionic cell according to claim 1, is characterized in that: described step 3) in electrostatic spraying solution time, voltage of electric field is 10 ~ 30kV, and receiving range is 5 ~ 15cm.
6. the preparation method of anode plate for lithium ionic cell according to claim 1, it is characterized in that: described step 5) in charing process time, carry out in high temperature carbonization furnace, in an inert atmosphere, with the programming rate of 1 ~ 20 DEG C/min from room temperature to 500 ~ 1000 DEG C, constant temperature 1 ~ 3h, after being then cooled to room temperature, taking out and obtains described negative plate.
7. the preparation method of anode plate for lithium ionic cell according to claim 1, it is characterized in that: described step 2) in, described polymer is the one or more kinds of mixtures in sucrose, soluble starch, citric acid, polyvinyl alcohol, polyvinylpyrrolidone, polyaniline, polypyrrole.
8. the anode plate for lithium ionic cell that obtains of a preparation method according to claim 1.
9. a lithium ion battery, is characterized in that: the negative plate of described lithium ion battery is negative plate as claimed in claim 8.
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