CN104073853A - Electro-deposition preparation of silicon-oxygen-carbon complex porous electrode for cathode of lithium ion battery - Google Patents
Electro-deposition preparation of silicon-oxygen-carbon complex porous electrode for cathode of lithium ion battery Download PDFInfo
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Abstract
The invention discloses electro-deposition preparation of a silicon-oxygen-carbon complex porous electrode for a cathode of a lithium ion battery. The preparation method comprises the following steps: firstly, preparing a porous nickel electroplate liquid; electroplating porous nickel on a working area of a planar metal current collector; then, dissolving tetrabutyl ammonium salt and a silicon compound in an organic carbonic ester solvent in an argon atmosphere in a glove box to prepare the electroplate liquid; finally, realizing co-deposition of silicon, oxygen and carbon on the porous nickel metal current collector by adopting a constant current electrodeposition method, then, taking and washing by an anhydrous organic solvent, and vacuum-drying to obtain the silicon-oxygen-carbon complex porous electrode for the cathode of the lithium ion battery. The scheme disclosed by the invention can be used for solving the problems that the plating thin film of the electrode of the lithium ion battery and the current collector are weak in bonding force, the silicon thin film is poor in conductivity, the film thickness is hard to increase and the like, so that the high capacity of the lithium ion battery and good circulating stability are guaranteed, the volume effect of silicon in lithiation process is alleviated, the electrochemical circulating performance of the electrode material is improved, and the commercialized application of the electrode is extremely promoted.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, the particularly galvanic deposit preparation of used as negative electrode of Li-ion battery silica carbon complex porous electrode in Organic Electricity plating solution.
Background technology
Current business-like lithium ion battery negative material adopts embedding lithium carbon material (the theoretical embedding lithium of graphite capacity is 372mAh/g) mostly, but the current potential of carbon dioxide process carbon electrode current potential and metallic lithium is very approaching, when battery overcharge, the easy precipitating metal lithium of carbon electrodes, formation dendrite pierces through barrier film and causes short circuit, and most electrolytic solution is unstable under this current potential, ionogen easily decomposes at electrode surface, produces inflammable gas mixture and causes safety problem.Although people attempt the carbon materials such as graphite to carry out modification, as adopt the New Type of Carbon electrodes such as micro-carbon pearl, refinery coke, carbon fiber, cracking carbon, but the problem that still exists voltage delay and circulation volume to decline, cannot meet the demand of lithium ion battery anticathode heavy body of future generation, one of key factor that therefore improves battery performance is just research and the application of heavy body negative material.Silicon materials are because having the highest theoretical embedding lithium capacity (4200mAh/g) and moderate doff lithium current potential (0.1～0.5V vs.Li/Li
+), and be considered to one of lithium ion battery negative material of most possible commercial applications, however silicon materials are at Li
+embedding and deviate from process to have serious volume effect, embedding lithium process cubical expansivity is about 300%, easily causes material structure avalanche and peel off so that lose electrically contacting, and causes electrode cycle performance sharply to decline.
In recent years, experts and scholars have launched extensive and deep research to pure silicon, silicon-base oxide, Si-M system (M represents activity or inert metal and compound), Si-C system and silica-base film material both at home and abroad, result shows in metal collector, to deposit certain thickness silica-base film material by the method for deposition, can effectively alleviate the volumetric expansion that alloying process causes, can effectively improve the cyclical stability of material, and be considered to optimal carbon negative pole equivalent material, therefore, a large amount of research is conceived to the research and development of silica-base film material.
Electrochemical Solid-State Letters magazine the 6th volume the 9th phase A198-A201 page in 2003 reported by magnetron sputtering method on Copper Foil respectively deposit thickness be the amorphous silicon membrane of 250nm and 1 μ m, thickness is that the amorphous silicon membrane of the 250nm specific storage after 30 times that circulates under C/2.5 multiplying power remains 3500mAh/g, higher reversible capacity and good cyclical stability show the good combination between sputtered silicon and Copper Foil substrate, and the amorphous silicon membrane that thickness is 1 μ m circulates under C/2.5 multiplying power, specific storage after 12 times remains 3000mAh/g, capacity is decayed fast subsequently, cyclical stability declines rapidly, result shows along with film thickness increases, irreversible capacity increases and special capacity fade, cyclical stability declines.
Journal of American Chemical Society magazine the 4th volume the 9th phase 5366-5372 page in 2010 has been reported by physical vaporous deposition and deposited skim silicon materials on the coated tobacco mosaic virus (TMV) array structure collector of stainless steel-based basal surface metallic nickel, tem analysis shows that depositing silicon is non-crystalline silicon, at room temperature under 0～1.5V different multiplying, carry out battery charging and discharging test, under different multiplying, circulate after 5～6 times, coulomb efficiency all can approach 100%, every circulation primary average capacity loss is 0.20% (1C), 0.46% (2C), 0.50% (4C), cyclic discharge capacity is 3343mAh/g (1C) for the second time, 2251mAh/g (2C), 1656mAh/g (4C), heavy body and good cycle performance are owing to this special three-dimensional nucleocapsid structure, in addition, thin layer non-crystalline silicon can effectively be alleviated the volumetric expansion of alloying process, also caused good cyclical stability.
Although adopt above-mentioned magnetron sputtering method and physical vaporous deposition to prepare silica-base film negative pole, can possess higher capacity and good cyclical stability, but material preparation to equipment have high requirements, cost is high, complex process and be difficult to prepare micron order thick film, be difficult to produce fast on a large scale.And on the other hand, for vapour deposition process, electro-deposition method is prepared that material is low for equipment requirements, cost is low and is easy and simple to handle, can carry out controlling diaphragm thickness by parameters such as regulate electrical current and the quantities of electric charge, and can there is heavy body and good cyclical stability, there is actual production meaning.Yet because siliceous deposits current potential is low and be easy to the reasons such as hydrolysis, be difficult to the silica-based alloy of galvanic deposit in conventional soln.Energy & Environmental Science magazine the 5th volume 6500-6505 page in 2012 reported on copper current collector and prepared silica-based complex thin film for the method for cathode of lithium battery by galvanic deposit, and this silica-base film negative pole still can keep capacity up to 800mAhg after thousands of circulations
-1.But the method still exist film and current collector bonding force a little less than, silicon film electroconductibility is poor, thickness is difficult to the problems such as increase, has greatly limited its commercial applications.
Summary of the invention
For defect of the prior art, the object of this invention is to provide a kind of galvanic deposit preparation of used as negative electrode of Li-ion battery silica carbon complex porous electrode.First prepare nickel porous electroplate liquid, on planar metal collector, electroplate one deck nickel porous, then in glove box, in argon atmosphere, 4-butyl ammonium and silicon-containing compound are dissolved in to organic carbonate ester solvent preparation electroplate liquid, finally adopt Constant Electric Current sedimentation on porous nickel metal collector, to realize the codeposition of silica carbon, then take out working electrode and rinse and vacuum-drying with anhydrous organic solvent, thereby obtain used as negative electrode of Li-ion battery silica carbon complex porous electrode.
The present invention is achieved by the following technical solutions:
The invention provides a kind of galvanic deposit preparation of used as negative electrode of Li-ion battery silica carbon complex porous electrode, comprise the steps:
(1) preparation of porous nickel metal collector: under 20～30 ℃ of conditions, take precious metal as anode, planar metal collector are negative electrode, carry out galvanic deposit in nickel porous electroplate liquid, depositing current density is 1～4A/dm
2, the time is 20～120s, obtains porous nickel metal collector;
(2) preparation of silica carbon complex porous electrode: silica carbon complex Organic Electricity plating solution is placed in to three electrode bottles; at glove box dew point lower than-100 ℃ and have under argon shield condition; take precious metal as reference electrode and being negative electrode to electrode, porous nickel metal collector, is 0.7～3.0mA/cm in apparent area current density
2, under the quantity of electric charge condition that is 6～10C, in silica carbon complex Organic Electricity plating solution, carry out galvanic deposit, prepare silica carbon complex porous electrode.
Preferably, the preparation of described step (1) nickel porous electroplate liquid is specially: at room temperature, ammonium salt and nickel salt are dissolved in to pure water and are mixed with nickel porous electroplate liquid, the concentration that makes ammonium salt in electroplate liquid is 1～2mol/L, the concentration of nickel salt is 0.1～0.3mol/L, and magnetic stirrer makes it to mix and get final product.
Preferably, described ammonium salt is ammonium chloride, and nickel salt is nickelous chloride.
Preferably, in described step (1), precious metal is platinum; Described planar metal collector is that working area is 1 * 1cm
2, the thickness copper sheet that is 0.1～0.2mm.
Preferably, the following pre-treatment of described step (1) midplane metal collector warp: be 3～5A/dm in current density
2under carry out the electrolytic degreasing of 30～60s, and be soaked in volume fraction and be 10～15s in 20% dilute sulphuric acid, clean by pure water rinsing.
Preferably; in described step (2), the preparation of silica carbon complex Organic Electricity plating solution is specially: under argon shield; 4-butyl ammonium is dissolved in to organic carbonate ester solvent; magnetic agitation 1～2h; add again silicon-containing compound; magnetic agitation 1～2h, the concentration that makes 4-butyl ammonium in electrolytic solution is 0.3～0.5mol/L, the concentration of silicon-containing compound is 0.3～0.5mol/L.
Preferably, in described step (2), precious metal is platinum.
Preferably, in described step (2), silica carbon complex porous electrode needs to rinse with anhydrous organic solvent after electrodeposition finishes, and then puts into vacuum chamber vacuum-drying 8～10h.
Preferably, described anhydrous organic solvent is methylcarbonate, NSC 11801 or propylene carbonate.
Due to the special construction of nickel porous and higher surfaceness, adopt the silica carbon complex of Constant Electric Current sedimentation codeposition and the adhesivity of nickel porous collector good, make in this silica carbon complex porous electrode without adding conductive additive and binding agent, reduced the impact of non-material factor on electrode performance, in battery charging and discharging circulation, silica carbon complex can keep not coming off with the good adhesion of nickel collector, has guaranteed heavy body and good cyclical stability.
There is irregular cavernous structure in porous nickel electrode surface, if form silica-base film by methods such as magnetron sputtering method or physical vaporous depositions in nickel porous, silica-base film can only be covered in the top layer of nickel porous and cannot enter into hole interior wall construction, in the present invention, in Organic Electricity plating solution, adopt electrodip process can guarantee that electroplate liquid infiltrates top layer and the hole interior wall construction of nickel porous, silica carbon complex not only can cover nickel porous top layer and can coverage hole interior wall construction.
The silica carbon complex that deposits preparation by Constant Electric Current not only can cover top layer but also can coverage hole interior wall construction, in battery charge and discharge process, the special construction in hole can be alleviated the volume effect of silicon in doff lithium process to a certain extent, improves the electrochemistry cycle performance of electrode materials.
Compared with prior art, the present invention has following beneficial effect:
(1) silicon film thickness of preparing by magnetron sputtering method, physical vaporous deposition is at present generally below 1 μ m, be difficult to prepare silicon thick film, and in the present invention, adopt electrodip process can prepare the silica-based thick film of micron order by controlling galvanic deposit parameter, for example, controlling apparent areal electric current density is 1mA/cm
2, the quantity of electric charge is 10C, can obtain the silica carbon thick film that thickness is about 2.5 μ m.
(2) this silica carbon complex porous electrode is after little electric current discharges and recharges activation, large current cycle first circle electric discharge (embedding lithium) capacity can reach 1408mAh/g, charging (de-lithium) capacity can reach 1105mAh/g, cycle efficiency can reach 78.5%, discharge and recharge after 100 times, charging capacity can reach 706.3mAh/g, and the average charge capability retention of each circulation is 98.8%, has good cyclical stability.
Accompanying drawing explanation
By reading the detailed description of non-limiting example being done with reference to the following drawings, it is more obvious that other features, objects and advantages of the present invention will become:
Fig. 1 is nickel porous SEM pattern;
Wherein, (a) 50 μ m, (b) 10 μ m, (c) 5 μ m, (d) 500nm;
Fig. 2 is silica carbon complex SEM pattern;
Wherein, (a) 50 μ m, (b) 10 μ m, (c) 5 μ m, (d) 500nm;
Fig. 3 is the STEM sign that nickel porous is electroplated silica carbon complex cross-sectional sample;
Wherein, (a) the STEM image of silica carbon complex, (b) represents selected area electron diffraction style in (a), (c) represents to select in (a) high resolution picture in region;
Fig. 4 is that silica carbon porous electrode first circle 0.05mA discharges and recharges activation and with after 0.2mA circulation 16 times, makes cyclic voltammetry curve again;
Fig. 5 is capacity-cycle index curve of battery charging and discharging circulation 100 times;
Fig. 6 is the charging and discharging curve of the 1st time, the 2nd time, the 10th time, the 50th time and the 100th time in 100 processes of battery charging and discharging circulation;
Fig. 7 is that silica carbon complex porous electrode becomes high rate performance test;
Fig. 8 is SEM pattern after the circulation of silica carbon complex porous electrode;
Wherein, first circle 0.05mA (a) discharges completely, (b) charging completely, charging completely after 100 circulations, (c) 20 μ m and (d) 5 μ m.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art further to understand the present invention, but not limit in any form the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
embodiment 1
The present embodiment provides a kind of galvanic deposit preparation of used as negative electrode of Li-ion battery silica carbon complex porous electrode, and further preparation effect is detected.
(1) at room temperature 53.49g ammonium chloride and 6.48g nickelous chloride are dissolved in to pure water, with magnetic stirring apparatus, constantly stir, be mixed with 500mL nickel porous electroplate liquid, wherein the volumetric molar concentration of ammonium chloride is 2mol/L, and the volumetric molar concentration of nickelous chloride is 0.1mol/L.
(2) at 25 ℃ of temperature, carry out the galvanic deposit of nickel porous, take metal platinum guaze as anode, thickness is that 0.1mm copper sheet is negative electrode, and the working area of using insulation tape strictly to control copper current collector is 1 * 1cm
2, before galvanic deposit, first by copper current collector electrolytic degreasing, current density is 3A/dm
2, the time is 40s, then with large water gaging, rinse well and the dilute sulphuric acid that is 20% in volume fraction in soak 15s, cleaner by pure water rinsing, finally adopt Constant Electric Current sedimentation to prepare nickel porous, control current density is 3A/dm
2, electrodeposition time is 60s, galvanic deposit finishes with pure water rinsing cold wind, to dry up afterwards, puts into vacuum chamber vacuum-drying 8～10h, the SEM figure that Fig. 1 is nickel porous.
(3) in glove box under argon shield; 6.84g tetrabutylammonium perchlorate is dissolved in to 37.7mL propylene carbonate solvent; magnetic agitation 1h; then measure 2.3mL silicon tetrachloride and join above-mentioned solution for continuous magnetic agitation 1h; finally be mixed with 40mL electroplate liquid; wherein tetrabutylammonium perchlorate's volumetric molar concentration is 0.5mol/L, and the volumetric molar concentration of silicon tetrachloride is 0.5mol/L.
(4) above-mentioned electroplate liquid is placed in to three electrode bottles; at glove box dew point lower than-100 ℃ and there is the galvanic deposit of carrying out silica carbon complex under argon shield condition; take nickel porous collector as working electrode; its working area is still 1 * 1cm2; high purity platinum filament is reference electrode and to electrode; before galvanic deposit, need porous nickel electrode to rest in electroplate liquid and soak 15min, then adopt Constant Electric Current sedimentation to prepare silica carbon complex, apparent area current density is 1.0mA/cm
2the galvanic deposit quantity of electric charge is 10C, after galvanic deposit finishes, take out working electrode and throw off insulation tape and rinse by dimethyl carbonate solvent, then put into vacuum chamber vacuum-drying 8～10h, just obtain a kind of used as negative electrode of Li-ion battery silica carbon complex porous electrode, Fig. 2 is that nickel porous is electroplated silica carbon complex SEM figure, can observe porous nickel surface and cover one deck silica carbon complex, nickel dendrite is coated by silica carbon complex, also fills to a certain extent upper silica carbon complex in hole.
(5) by focused ion beam technology, nickel porous is electroplated to silica carbon complex and be prepared into cross-sectional sample, use STEM (JEM-2100F) to carry out composition and structure sign, as shown in Figure 3, silica carbon complex is carried out to selected area electron diffraction, there is a center spot of dispersing in Fig. 3 (b), the existence form that has disclosed silicon in this mixture is non-crystalline state, in Fig. 3 (c) presentation graphs 3 (a), select the high resolution picture in region, show that in silica carbon complex, silicon is non-crystalline state and is surrounded by Organic Electricity plating solution degradation production.
(6) adopt lithium hexafluoro phosphate electroplate liquid to carry out cycle performance of battery test, in three electrode bottles, add 40mL electroplate liquid, it is working electrode that the nickel porous of take is electroplated silica carbon complex, and metallic lithium is reference electrode and to electrode.Cyclic voltammetry carries out (Shanghai Hua Chen Instrument Ltd. provides) on CHI660E electrochemical workstation, and voltage change scope is 0.01～1.5V vs.Li/Li+, and sweep velocity is 0.1mV/s.Cycle performance of battery carries out on battery test system (Shenzhen Ke Jingzhida Science and Technology Ltd. provides), discharges and recharges stopping potential with respect to Li/Li
+be 0.01～1.20V, first charge-discharge recycles the little electric current of 0.05mA, and object is to activate electroplate liquid, and charge and discharge cycles electric current is set to 0.2mA afterwards.
Silica carbon complex porous electrode is carried out to cyclic voltammetry, before test, first silica carbon porous electrode is carried out to circulating battery as negative pole, first circle 0.05mA charge and discharge cycles is with activation electroplate liquid, use again 0.2mA current cycle 16 times, then in glove box, use CHI660E electrochemical workstation to carry out cyclic voltammetry, result as shown in Figure 4.From cyclic voltammetry curve, silica carbon complex embedding lithium plateau potential is about 0.1515V and 0.0112V, de-lithium plateau potential is about 0.3560V and 0.5029V, and the 0.2840V cathodic reduction peak occurring in curve and 0.7221V anodic oxidation peak are owing to porous Ni substrate, may be that nickel oxide doff lithium process just can produce extra peak position in cyclic voltammetry curve because nickel porous is oxidized.
Silica carbon complex porous electrode is carried out to cycle performance of battery test as negative pole, and first circle is used 0.05mA current activation, uses afterwards 0.2mA electric current charge and discharge cycles 100 times.Fig. 5 is capacity-cycle index curve of battery charging and discharging circulation 100 times, adopt the first charge-discharge circulation of 0.2mA electric current, as battery first circle circular treatment, electric discharge (embedding lithium) capacity can reach 1408mAh/g, and charging (de-lithium) capacity can reach 1105mAh/g, and cycle efficiency can reach 78.5%, continuation circulates 100 times under same electric current, charging capacity can reach 706.3mAh/g, with respect to first circle charging capacity conservation rate, is 64%, has good cyclical stability.
Fig. 6 is the charging and discharging curve of the 1st, 2,10,50,100 times in battery charging and discharging working cycle, capacity and voltage curve from electric discharge (embedding lithium) process, in silicon, the plateau potential of embedding lithium is 0.1515V and 0.0112V, and from capacity and the voltage curve of charging (de-lithium) process, in silicon, the plateau potential of de-lithium is 0.3560V and 0.5029V, and this is consistent with the result of cyclic voltammetry.
Fig. 7 is that nickel porous is electroplated the test of silica carbon complex change high rate performance, first circle discharges and recharges to activate electroplate liquid with 0.05mA electric current, afterwards respectively with 0.2mA, 0.4mA, 0.6mA, 0.8mA, 1.0mA, 0.4mA electric current charge and discharge cycles 10 times, obtain cell container as shown in Figure 7 with the zoom rate curve of cycle index, can find that nickel porous plating silica carbon complex electrode is at 0.5C, 1.5C, 3C, 6C, 10C, under multiplying power, reversible charging capacity remains on respectively 992.7mAh/g, 766mAh/g, 637.7mAh/g, 465mAh/g, 265.3mAh/g, when dropping to 1.5C multiplying power from 10C multiplying power, reversible loading capacity still remains on 737mAh/g, nickel porous is electroplated the high electrochemical performance of silica carbon complex electrode owing to the high conductivity of the nickel dendrite of coated silica carbon, the very big degree of surface-area and energy is alleviated the irregular cavernous structure of volume effect in active material silicon doff lithium process greatly.
For the further circulating battery of analyzing affects the pattern of silica carbon complex porous electrode, respectively the sample after first circle 0.05mA electric discharge and charging is made to SEM morphology analysis, as Fig. 8 (a) and (b).Fig. 8 (a) shows after embedding lithium, to cause volumetric expansion completely in silicon, quantity and the diameter in hole are all significantly reduced, surface produces some crackles, Fig. 8 (b) shows that lithium ion deviates to make silicon Study of Volume Expansion to disappear from silicon, but the quantity in hole and diameter almost do not change, this has also explained silicon materials irreversible capacity loss first greatly to a certain extent.Meanwhile, also silica carbon complex porous electrode is continued to use after the activation of 0.05mA first circle 0.2mA current cycle to carry out SEM morphology analysis 100 times, as Fig. 8 (c) and (d), Fig. 8 (c) is the image under low enlargement ratio, quantity and the diameter that can obviously observe hole still significantly reduce before circulation, because the volume effect of silicon doff lithium process causes in hole being filled in various degree, and material surface produces many fine cracks, in Fig. 8 (d), can clearly observe tiny crack, this has also explained the capacitance loss of silica carbon complex porous electrode in 100 working cyclees, on the other hand, silica carbon complex still can be good at keeping three-dimensional porous structure after 100 circulations, structural stability and the cyclical stability of silica carbon complex porous electrode excellence have also been described.
embodiment 2
The present embodiment provides a kind of galvanic deposit preparation of used as negative electrode of Li-ion battery silica carbon complex porous electrode, is with the difference of embodiment 1:
In step (1), the volumetric molar concentration of ammonium chloride is 1mol/L, and the volumetric molar concentration of nickelous chloride is 0.3mol/L;
In step (2), temperature is 20 ℃, and copper sheet thickness is 0.2mm, and the current density of electrolytic degreasing is 5A/dm
2, the time is 30s, soaks 10s in dilute sulphuric acid, galvanic deposit current density is 1A/dm
2, electrodeposition time is 20s;
In step (3), organic carbonate ester solvent is NSC 11801, and tetrabutylammonium perchlorate's volumetric molar concentration is 0.3mol/L, and the volumetric molar concentration of silicon tetrachloride is 0.3mol/L;
In step (4), before galvanic deposit, porous nickel electrode is rested in electroplate liquid and soaks 20min, apparent area current density is 3.0mA/cm
2, deposited charge amount is 6C, anhydrous organic solvent is NSC 11801.
embodiment 3
The present embodiment provides a kind of galvanic deposit preparation of used as negative electrode of Li-ion battery silica carbon complex porous electrode, is with the difference of embodiment 1:
In step (1), the volumetric molar concentration of ammonium chloride is 1.5mol/L, and the volumetric molar concentration of nickelous chloride is 0.2mol/L;
In step (2), temperature is 30 ℃, and copper sheet thickness is 0.15mm, and the current density of electrolytic degreasing is 4A/dm
2, the time is 60s, soaks 12s in dilute sulphuric acid, galvanic deposit current density is 4A/dm
2, electrodeposition time is 120s;
In step (3), tetrabutylammonium perchlorate's volumetric molar concentration is 0.4mol/L, and the volumetric molar concentration of silicon tetrachloride is 0.4mol/L;
In step (4), before galvanic deposit, porous nickel electrode is rested in electroplate liquid and soaks 17min, apparent area current density is 2.0mA/cm
2, deposited charge amount is 8C.
Above specific embodiments of the invention are described.It will be appreciated that, the present invention is not limited to above-mentioned specific implementations, and those skilled in the art can make various distortion or modification within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (9)
1. the galvanic deposit of used as negative electrode of Li-ion battery silica carbon complex porous electrode preparation, is characterized in that, comprises the steps:
(1) preparation of porous nickel metal collector: under 20～30 ℃ of conditions, take precious metal as anode, planar metal collector are negative electrode, carry out galvanic deposit in nickel porous electroplate liquid, depositing current density is 1～4A/dm
2, the time is 20～120s, obtains porous nickel metal collector;
(2) preparation of silica carbon complex porous electrode: silica carbon complex Organic Electricity plating solution is placed in to three electrode bottles; at glove box dew point lower than-100 ℃ and have under argon shield condition; take precious metal as reference electrode and being negative electrode to electrode, porous nickel metal collector, is 0.7～3.0mA/cm in apparent area current density
2, under the quantity of electric charge condition that is 6～10C, in silica carbon complex Organic Electricity plating solution, carry out galvanic deposit, prepare silica carbon complex porous electrode.
2. the galvanic deposit of used as negative electrode of Li-ion battery silica carbon complex porous electrode according to claim 1 preparation, it is characterized in that, the preparation of described step (1) nickel porous electroplate liquid is specially: at room temperature, ammonium salt and nickel salt are dissolved in to pure water and are mixed with nickel porous electroplate liquid, the concentration that makes ammonium salt in electroplate liquid is 1～2mol/L, the concentration of nickel salt is 0.1～0.3mol/L, and magnetic stirrer makes it to mix and get final product.
3. the galvanic deposit of used as negative electrode of Li-ion battery silica carbon complex porous electrode according to claim 2 preparation, is characterized in that, described ammonium salt is ammonium chloride, and described nickel salt is nickelous chloride.
4. the galvanic deposit of used as negative electrode of Li-ion battery silica carbon complex porous electrode according to claim 1 preparation, is characterized in that, in described step (1), precious metal is platinum; Described planar metal collector is that working area is 1 * 1cm
2, the thickness copper sheet that is 0.1～0.2mm.
5. the galvanic deposit of used as negative electrode of Li-ion battery silica carbon complex porous electrode according to claim 1 preparation, is characterized in that, the following pre-treatment of described step (1) midplane metal collector warp: be 3～5A/dm in current density
2under carry out the electrolytic degreasing of 30～60s, and be soaked in volume fraction and be 10～15s in 20% dilute sulphuric acid, clean by pure water rinsing.
6. the galvanic deposit of used as negative electrode of Li-ion battery silica carbon complex porous electrode according to claim 1 preparation; it is characterized in that; in described step (2), the preparation of silica carbon complex Organic Electricity plating solution is specially: under argon shield; 4-butyl ammonium is dissolved in to organic carbonate ester solvent; magnetic agitation 1～2h; add again silicon-containing compound; magnetic agitation 1～2h; the concentration that makes 4-butyl ammonium in electroplate liquid is 0.3～0.5mol/L, and the concentration of silicon-containing compound is 0.3～0.5mol/L.
7. the galvanic deposit of used as negative electrode of Li-ion battery silica carbon complex porous electrode according to claim 1 preparation, is characterized in that, in described step (2), precious metal is platinum.
8. the galvanic deposit of used as negative electrode of Li-ion battery silica carbon complex porous electrode according to claim 1 preparation, it is characterized in that, in described step (2), silica carbon complex porous electrode rinses with anhydrous organic solvent after galvanic deposit finishes, and then puts into vacuum chamber vacuum-drying 8～10h.
9. the galvanic deposit of used as negative electrode of Li-ion battery silica carbon complex porous electrode according to claim 8 preparation, is characterized in that, described anhydrous organic solvent is methylcarbonate, NSC 11801 or propylene carbonate.
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| CN111919313A (en) * | 2018-02-26 | 2020-11-10 | 格拉芬尼克斯开发公司 | Anode for lithium-based energy storage devices |
| CN115000348A (en) * | 2022-05-23 | 2022-09-02 | 上海交通大学 | Alkali metal negative electrode composite coating and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111919313A (en) * | 2018-02-26 | 2020-11-10 | 格拉芬尼克斯开发公司 | Anode for lithium-based energy storage devices |
| CN115000348A (en) * | 2022-05-23 | 2022-09-02 | 上海交通大学 | Alkali metal negative electrode composite coating and preparation method and application thereof |
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