CN105489839A - Copper-silicon negative electrode and preparation method therefor - Google Patents
Copper-silicon negative electrode and preparation method therefor Download PDFInfo
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- CN105489839A CN105489839A CN201410475617.9A CN201410475617A CN105489839A CN 105489839 A CN105489839 A CN 105489839A CN 201410475617 A CN201410475617 A CN 201410475617A CN 105489839 A CN105489839 A CN 105489839A
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Abstract
The invention relates to a preparation method for a negative plate, and provides a copper-silicon negative electrode and a preparation method therefor. A negative electrode active material contains silicon; and the negative electrode active material is welded on a current collector through metal. According to the copper-silicon negative electrode, the electrode active material is welded on the surface of the current collector through metal, so that the negative plate is endowed with excellent metal conductivity; the negative plate is directly welded through the metal and a silicon-copper composite material, so that the action force among the materials is high without causing a peel-off phenomenon of the active substance; the negative plate is prepared from the metal and the silicon-copper composite material, so that the prepared negative plate can be well compressed, the thickness of a pole piece is thinned, and the volume energy density of the battery is improved consequently.
Description
Technical field
The invention belongs to field of lithium ion battery, relate to a kind of cathode pole piece and preparation method thereof, be specifically related to copper silicium cathode and preparation method thereof.
Background technology
Current business-like lithium ion battery is widely used in the fields such as mobile phone, portable equipment, public transport equipment, and these lithium ion batteries are by compositions such as anode pole piece, barrier film, cathode pole piece, electrolyte solution and shells.The material that positive pole adopts mainly contains LiCoO
2, LiNiO
2, LiMn
2o
4, LiFePO
4, NCM, NCA etc. containing the composite metal oxide of lithium, these materials have the advantages such as long compared with height ratio capacity, higher operating voltage, life-span.The negative pole corresponding with above-mentioned positive electrode generally adopts graphite, lithium titanate Li
4ti
5o
12, the material such as silicon.
The preparation method of current conventional anode pole piece adopts active material, binding agent, conductive agent, solvent to prepare slurry to be applied to copper current collector and to make.
The advantage of graphite cathode is embedding and deintercalation that its layer structure is conducive to lithium ion, and itself conducts electricity very well.Shortcoming is that the binding agent added is insulation, and because this reducing the conductivity of negative pole, and negative plate works long hours and Swelling can occur in electrolyte solution, causes active material to come off, and reduces its cycle life; Its schungite is combustibles, there is larger potential safety hazard.Carry out the mainly Chuan Ya Dynamics Co., Ltd of this aspect research at present, the Chinese patent application (publication number is 103078089A) of its application improves material volume energy density and chemical property by composite graphite negative electrode.
The advantage of lithium titanate negative active material is it is zero strain material, and good cycle, discharging voltage balance, cycle life is longer.Its shortcoming is the metal_based material of specific capacity lower than other, theoretical capacity 175mAh/g, and polarization phenomena that its conductivity is low when causing heavy-current discharge are relatively more serious, and thus under high magnification, performance is not good; In addition, lower as its tap density of battery material, the capacity of unit volume is less, and owing to adopting binding agent can produce swelling and reduce its conductivity.Current Duo-fluoride Chemicals Co., Ltd. (publication number is 102916170A) and Shanghai University's (publication number is 102820461A) all improve high rate performance by the coated lithium titanate of carbon and improve conductivity performance.
Silicon materials have larger storage lithium specific capacity (4200mAh/g), and silicon rich content on earth, be negative material very desirable in research at present.But when silicon materials are as negative pole, in charging process, lithium ion can arrive negative pole from positive electrode and silicon materials form Li-Si alloy.Now a silicon can form alloy with four lithiums thus provide very large capacity, and corresponding volume meanwhile can be caused to increase; And when discharging, the lithium in Li-Si alloy departs from and moves to positive pole and goes, and can cause the volume-diminished of Li-Si alloy simultaneously.The reversible behavior sharply increasing and reduce of this volume can cause the structural instability of Li-Si alloy, the original structure of silicon materials is destroyed and the coming off of electrode material, thus make first charge-discharge efficiency low, contact variation between electrode material with collector.
At present for improving the lithium ion efficiency for charge-discharge of silicium cathode material, mainly through changing the composition of silicium cathode material, the Chinese patent application (publication number is 103682268A) of such as Shanghai application National Engineering Research Centre Co., Ltd, by silicon face carbon coated and lithium titanate, thus improve efficiency for charge-discharge.But these methods improve more limited to the efficiency of silicium cathode material, and cycle performance is unsatisfactory.
Anode plate for lithium ionic cell, especially the preparation of the negative plate of silicium cathode active material is adopted mostly to adopt above-mentioned conventional method, the adhesive that the method adopts is generally organic polymer, reduce the conductivity of pole piece, and the swelling meeting of volume occurs silicon materials in charge and discharge process irreversible change and binding agent causes coming off of material, have a strong impact on the performance of lithium ion battery.
Summary of the invention
For solving the problems of the technologies described above, the present invention first object is to provide a kind of copper silicium cathode, comprises negative active core-shell material and collector, and described negative active core-shell material is siliceous, described negative active core-shell material by metal solder on collector.
The present invention adopts Large Copacity silicon as active material, and the high-capacity material that commercialization can be provided to need, ensure that high-energy-density; Secondly, the present invention adopts metal simple-substance as welding compound, has more excellent conductivity, can ensure to work under high current density than the conductive black etc. adopted at present; In addition, because copper silicon composite is welded direct on collector by metal, the adhesion of copper silicium cathode and collector is comparatively large, and the peeling phenomenon of active material can not occur; Finally, owing to adopting metal simple-substance and copper silicon compound to prepare negative pole, good compacting can be carried out to the negative pole of preparation, greatly reduce pole piece thickness, thus mention the volume energy density of battery.
As preferably, described negative active core-shell material is silicon or copper silicon compound.
As preferably, in described copper silicon compound, the content of silicon is 5wt% ~ 80wt%.As preferred further, in described copper silicon compound, the content of silicon is 10wt% ~ 60wt%.As further preferred, in described copper silicon compound, the content of silicon is 20wt% ~ 40wt%.
As preferably, described copper silicon compound is prepared from by silicon and mantoquita.As preferred further, described metallic copper is formed by reducing substances reduction copper compound.
As preferably, described mantoquita is at least one in copper sulphate, Schweinfurt green, copper nitrate, acetylacetone copper and copper chloride; Described mantoquita can water-soluble and/or ethanol.
As preferably, described metal is metallic copper.The metal of welding compound of the present invention also can be that other does not form the metal of alloy, as gold, silver etc. with lithium.As preferred further, described metallic copper is formed by reducing substances reduction copper compound.
As preferably, described reducing substances is reducing atmosphere and/or bonding reducing agent; Described bonding reducing agent is the polymer containing C, H, O.In welding process, reducing atmosphere such as hydrogen, carbon monoxide etc. can serve as reducing atmosphere.In addition, due to high temperature action during welding, the present invention is decomposed to form reproducibility carbon containing the polymer of C, H, O when welding and also described copper compound can be reduced into copper metal simple-substance and becomes welding compound; Welding terminates the rear described polymer containing C, H, O and can be removed because pyrolysis forms gas, thus improves the conductivity of the negative plate of preparation.
As preferably, described copper compound is at least one in cupric oxide, cuprous oxide, Kocide SD, copper nitrate and Schweinfurt green.Copper compound of the present invention directly can be bought from market and also can synthesize voluntarily.
As preferably, the particle diameter of described silicon is less than 5 μm.As preferred further, the particle diameter of described silicon is less than 1 μm.
As preferably, described collector is Copper Foil or foam copper.As preferred further, the thickness of described collector is 10 ~ 50 μm.As further preferred, the thickness of described collector is 25 ~ 50 μm.
Another object of the present invention is to provide the preparation method of above-mentioned copper silicium cathode, comprises following preparation process:
A, a pole piece preparation: copper silicon compound, bonding reducing agent, solvent form slurry are coated an obtained pole piece on collector;
Prepared by b, copper silicium cathode: be positioned in inert atmosphere by an above-mentioned pole piece and carry out reduction welding, namely obtain described copper silicium cathode after welding terminates.
Copper silicon compound, bonding reducing agent, solvent form slurry are coated collection liquid surface and dry; weld after oven dry; carry out under inert gas shielding in welding; copper silicon compound is welded on described collector and forms solder bond by reduction limit, limit, and the copper in the technical program in copper silicon compound uses as welding compound.Negative plate of the present invention, owing to adopting metal material by high temperature reduction and welding, therefore, still have a large amount of spaces between metal material and collector, activated silica material can be good at being scattered in these holes; In addition, due to the ductility that metal is good, expansion and contraction that silicon materials can not be undue can be protected fully, greatly improve the cycle life of lithium battery.
As preferably, in described slurry, also comprise copper compound or copper powder.The present invention can be that C reduces copper compound and obtains copper powder as welding compound by the bonding reducing agent Pintsch process in slurry in welding, and now, bonding reducing agent plays adhesive and reducing agent two effect; Using also can by directly adding copper powder as welding compound, and now, bonding reducing agent only uses as adhesive, is decomposed at subsequent high temperature.
As preferably, the quality bonding reducing agent described in a pole piece preparation is 5% ~ 30% of the gross mass of copper compound and copper silicon compound.
As preferably, in the preparation of copper silicium cathode, during reduction welding, pass into reducing atmosphere.Need in welding, to pass into reducing atmosphere again according to the consumption of welding compound when welding in actual industrial production, the addition of bonding reducing agent and working condition etc., as carbon monoxide, hydrogen, methane etc. play reduction further, increase reducing agent during welding; In addition, adding of reducing atmosphere can ensure again to be reduced to copper after the part copper of bonding reducing agent reduction is oxidized, improves welding effect further.
As preferably, in the preparation of copper silicium cathode, welding temperature is 400 ~ 1000 DEG C; Weld time is 0.1 ~ 10 hour.When this temperature can ensure that reducing agent is polymer, its carbon decomposited in reduction process can react as oxygen etc. with other elements and be pulled away, and improves the electrical property of follow-up negative pole.
As preferably, in the preparation of copper silicium cathode, welding temperature is 500 ~ 900 DEG C; Weld time is 0.5 ~ 6 hour.
As preferably, in the preparation of copper silicium cathode, a pole piece carries out precompressed before putting into inert atmosphere; The pressure of described precompressed is 0.2 ~ 20MPa/cm
2.
As preferably, weld in the preparation of copper silicium cathode after terminating and carry out final pressure; The pressure of described final pressure is 0.2 ~ 20MPa/cm
2.The present invention all carries out roll extrusion before or after pole piece welding, and active material thickness can be made after roll extrusion to reduce, and such as thickness reduces 30% to 50%, but is not restricted to this thickness.
As preferably, bonding reducing agent described in a pole piece preparation is at least one in polyacrylic acid, polyethylene glycol and acrylic resin.
Preferably progressive as one, the preparation method of described copper silicon compound comprises the following steps:
(1), a preparation copper silicon compound: mantoquita, silicon, surfactant and solvent are configured to suspension-turbid liquid, then the obtained copper silicon compound of suspension-turbid liquid described in spraying dry; (2) copper silicon compound, is prepared: obtain described copper silicon compound with the above-mentioned copper silicon compound of reducing agent reduction.Reducing agent of the present invention can select reducing substances of the present invention, namely can be reducing atmosphere and/or the polymer containing C, H, O.
In the present invention, the Main Function of surfactant is that silicon and mantoquita are evenly distributed.Mantoquita, silicon and surfactant are dissolved in solvent and carry out spraying dry, carry out reduction reaction after drying, by hydrogen or other reducing agent, mantoquita is reduced to copper in reduction reaction, copper and silicon are compounded to form copper silicon compound.In addition, the copper that this reduction reaction is formed also can play the effect of welding compound in follow-up welding process.
As preferably, described in a copper silicon compound preparation, solvent is at least one in water, methyl alcohol and ethanol.
As preferably, described in a pole piece preparation, solvent is at least one in water, methyl alcohol and ethanol.
As preferably, described in the preparation of copper silicon compound, reducing agent is at least one in carbon, hydrogen, carbon monoxide, methane, ethane, propane, methyl alcohol, ethanol and acetone.
As preferably, described in a copper silicon compound preparation, the quality of surfactant is 0% ~ 225% of copper quality in copper silicon compound.Namely surfactant of the present invention can play peptizaiton also can play reducing agent effect.
As preferably, surfactant described in a copper silicon compound preparation is the polymer containing C, H, O.As preferably, described in a copper silicon compound preparation, surfactant is at least one in polyacrylic acid, polyethylene glycol and polymethyl acrylate.
As preferably, described in a copper silicon compound preparation, surfactant is polyacrylic acid.
As preferably, in a copper silicon compound preparation, spray-dired temperature is 100 DEG C ~ 200 DEG C.
As preferably, in the preparation of copper silicon compound, during reducing agent reduction, temperature controls to be 200 ~ 800 DEG C.During reduction, the time preferably controls to be 5 ~ 7 hours.Time and temperature can regulate as required.In the present invention, the cooperation of the temperature and time of reduction reaction can ensure that the copper in mantoquita is reduced.Temperature herein can not be too high, and the time can not be oversize, because this can cause the copper generation crystal growth of reduction and bond to produce departing from, cannot form copper silicon compound; The temperature at this place can not be too low, the too low preparation that can affect copper silicon compound.
As preferred further, in the preparation of copper silicon compound, during reducing agent reduction, temperature controls to be 250 ~ 500 DEG C.
Another object of the present invention is to provide the preparation method of above-mentioned copper silicium cathode, comprises following preparation process:
A, pole piece preparation: by silica flour, bonding reducing agent, solvent, and copper compound or copper powder are mixed into slurry and coat an obtained pole piece on collector;
Prepared by b, copper silicium cathode: be positioned in inert atmosphere by an above-mentioned pole piece and carry out reduction welding, namely obtain described copper silicium cathode after welding terminates.
As preferably, the quality bonding reducing agent described in a pole piece preparation is 5% ~ 50% of silicon and copper compound gross mass.
As preferably, the quality bonding reducing agent described in a pole piece preparation is 5% ~ 50% of silicon and copper powder gross mass.
As preferably, in the preparation of copper silicium cathode, during reduction welding, pass into reducing atmosphere.Need in welding, to pass into reducing atmosphere again according to the consumption of welding compound when welding in actual industrial production, the addition of bonding reducing agent and working condition etc., as carbon monoxide, hydrogen, methane etc. play reduction further, increase reducing agent during welding; In addition, adding of reducing atmosphere can ensure again to be reduced to copper after the part copper of bonding reducing agent reduction is oxidized, improves welding effect further.
As preferably, in the preparation of copper silicium cathode, welding temperature is 400 ~ 1000 DEG C; Weld time is 0.1 ~ 10 hour.When this temperature can ensure that reducing agent is polymer, its carbon decomposited in reduction process can react as oxygen etc. with other elements and be pulled away, and improves the electrical property of follow-up negative pole.
As preferably, in the preparation of copper silicium cathode, welding temperature is 500 ~ 900 DEG C; Weld time is 0.5 ~ 6 hour.
As preferably, in the preparation of copper silicium cathode, a pole piece carries out precompressed before putting into inert atmosphere; The pressure of described precompressed is 0.2 ~ 20MPa/cm
2.
As preferably, weld in the preparation of copper silicium cathode after terminating and carry out final pressure; The pressure of described final pressure is 0.2 ~ 20MPa/cm
2.The present invention all carries out roll extrusion before or after pole piece welding, and active material thickness can be made after roll extrusion to reduce, and such as thickness reduces 30% to 50%, but is not restricted to this thickness.
As preferably, bonding reducing agent described in a pole piece preparation is at least one in polyacrylic acid, polyethylene glycol and acrylic resin.
Last object of the present invention is to provide a kind of lithium ion battery, comprises copper silicium cathode as above.
Technique effect
Copper silicium cathode provided by the invention, has the following advantages compared with the pole piece prepared with prior art: (1) adopts metallic welding electrode active material to collection liquid surface, and negative plate has the good electric conductivity of metal; (2) directly preparing cathode pole piece owing to adopting metal to weld with material, comparatively greatly, can not there is the peeling phenomenon of active material in the active force of storeroom; (3) owing to adopting metal and preparing with material, can good compacting be carried out to the cathode pole piece of preparation, reduce pole piece thickness, thus improve the volume energy density of battery; (4) this integrated battery cathode sheet will improve the conductivity of negative plate after bonding reducing agent and surfactant calcining removing.
Accompanying drawing explanation
The button cell test result figure that copper silicium cathode prepared by Fig. 1 embodiment of the present invention 1 makes;
The button cell test result figure that copper silicium cathode prepared by Fig. 2 embodiment of the present invention 2 makes;
The button cell test result figure that copper silicium cathode prepared by Fig. 3 embodiment of the present invention 3 makes;
The button cell test result figure that copper silicium cathode prepared by Fig. 4 embodiment of the present invention 4 makes;
The button cell test result figure that copper silicium cathode prepared by Fig. 5 embodiment of the present invention 5 makes.
Specific embodiment
Following specific embodiment is to invention has been detailed description, but the present invention is not restricted to following examples.Those skilled in the art can regulate raw material and proportioning thereof according to needs.
Embodiment 1
The preparation of copper silicon compound active material: copper acetate (31g) is dissolved in the mixed solution of absolute ethyl alcohol and deionized water as copper source completely, taking silica flour (6g) joins in the mixed solution of copper acetate, is finally joined in above-mentioned solution as surfactant by the polyacrylic acid aqueous solution (6g).Select spraying dry to prepare composite material to the solution configured, spraying dry selects nitrogen atmosphere, carries out at 160 DEG C.Then composite material is kept under an atmosphere of hydrogen 300 DEG C, 6h occur reduction reaction prepare copper silicon compound.
Prepared by metallic compound cupric oxide: the ammonia spirit taking 40g Schweinfurt green or copper organic acid salting liquid, water, 31g, by above-mentioned aqueous solution, the solution of mixing is carried out spraying dry at 180 DEG C, in air, prepares Cu (OH)
2powder, by Cu (OH)
2powder 200 DEG C, keep preparing CuO, Cu after 6h
2o powder.
The preparation of copper silicon compound pole piece: blended anode material copper silicon compound (0.6g), metallic compound cupric oxide (0.2g), bonding reducing agent PAA (polyacrylic acid) aqueous solution (0.6g), deionized water (2g) prepare slurry, and slurry curtain coating is applied to collector Cu paper tinsel surface and prepares pole piece and dry.
Pole piece welds: carry out 5MPa/cm to above-mentioned pole piece
2be positioned over after precompressed (nitrogen atmosphere) in stove, keep 6h to carry out welding pole piece is welded successfully at 500 DEG C.Final pressure compacting (1MPa/cm is carried out to pole piece after welding
2) after prepare diameter 14mm disk for assembling button cell (negative pole selects lithium sheet).Button cell test result as shown in Figure 1.As shown in Figure 1, first charge-discharge efficiency: 79.1%.First discharge specific capacity: 946mAh/g (with the Mass Calculation of copper silicon compound, the copper-clad herein in copper silicon compound draws together the copper that welding compound enters).
Embodiment 2
The preparation of copper silicon compound is with embodiment 1, and cupric oxide preparation is with embodiment 1.
The preparation of copper silicon compound pole piece: copper silicon compound (0.3g), cupric oxide (0.1g), bonding reducing agent Aqueous Solutions of Polyethylene Glycol (2g) are mixed with slurry, coat slurry onto on Cu paper tinsel collector and prepare pole piece, pole piece is dried and adopts 10MPa/cm
2pressure precompressed.
Pole piece welds: be positioned over by above-mentioned pole piece in the stove of logical nitrogen, at 500 DEG C, keep 6h to weld, then logical hydrogen reducing 2h at 300 DEG C, then at 5MPa/cm
2pressure under final pressure compacting pole piece, be cut into the disk that diameter is 14mm, for assembling button cell (lithium sheet do to electrode).The test result that button cell is surveyed as shown in Figure 2.First charge-discharge efficiency is 85.57% as seen from Figure 2.First discharge specific capacity is 927mAh/g (with the Mass Calculation of copper silicon compound, the copper-clad herein in copper silicon compound draws together the copper that welding compound enters).
Embodiment 3
The preparation of copper silicon compound active material: by copper acetate (31g) for copper source is dissolved in the mixed solution of absolute ethyl alcohol and deionized water, taking silicon (2.5g) joins in the mixed solution of copper acetate, is finally joined in above-mentioned mixed solution as surfactant by the polyacrylic acid aqueous solution (6g).Select spraying dry to prepare composite material to the mixed solution configured, spraying dry selects nitrogen atmosphere, and temperature is 160 DEG C; Then this composite material keep under an atmosphere of hydrogen 300 DEG C, 6h occur reduction reaction prepare copper silicon compound.The copper powder preparing copper silicon compound can simultaneously as welding compound.
The preparation of copper silicon compound pole piece: blended anode material copper silicon compound (0.8g), the PAA aqueous solution (0.3g) and deionized water (1g) prepare slurry, slurry is applied to collector Cu paper tinsel surface to be prepared pole piece and dries.
Pole piece welds: above-mentioned pole piece is positioned over (atmosphere of hydrogen) in stove, keeps 6h to carry out welding pole piece is welded successfully at 500 DEG C.Compacting (1MPa/cm is carried out to pole piece after welding
2) after prepare diameter 14mm disk for assembling button cell (negative pole selects lithium sheet).Button cell test result as shown in Figure 3.As shown in Figure 3, measure charging and discharging capacity with copper silicon compound (copper-clad herein in copper silicon compound draws together the copper that welding compound enters), first discharge specific capacity is: 673mAh/g, first discharging efficiency 71.3%, current density 0.0325mA/cm now
2.In addition, it can also be seen that from Fig. 1, when current density becomes 0.065mA/cm
2time, discharge capacity is 448mAh/g, and after 13 circulations, specific discharge capacity is 438mAh/g.
Embodiment 4
The preparation of copper silicon compound active material: be that copper source (31g) is dissolved in the mixed solution of absolute ethyl alcohol and deionized water by copper acetate, take silicon (6) and join in the mixed solution of copper acetate.Select spraying dry to prepare composite material to the solution configured, spraying dry selects nitrogen atmosphere, temperature control be 160 DEG C, then above-mentioned composite material is kept under an atmosphere of hydrogen 300 DEG C, 6h occur reduction reaction prepare copper silicon compound.
Prepared by metallic compound cupric oxide: the ammonia spirit taking 40g Schweinfurt green or copper organic acid salting liquid, water, 31g, becomes suspension solution by above-mentioned aqueous solution and carry out spraying dry under 180 °, in air, preparing Cu (OH)
2powder, by Cu (OH)
2powder, at 200 DEG C, keeps 6h to prepare CuO, Cu
2o powder.
The preparation of copper silicon compound pole piece: the aqueous solution (2g) of blended anode material copper silicon compound (0.3g), metallic compound cupric oxide (0.1g), adhesive polyethylene glycol prepares slurry, slurry is applied to collector Cu paper tinsel surface to be prepared pole piece and dries.
Pole piece welds: carry out 2MPa/cm to above-mentioned pole piece
2be positioned over after precompressed (nitrogen atmosphere) in tube furnace, keep 6h to carry out welding pole piece is welded successfully at 500 DEG C.Final pressure compacting (1MPa/cm is carried out to pole piece after welding
2) after prepare diameter 14mm disk for assembling button cell (negative pole selects lithium sheet).Button cell test result as shown in Figure 4.As shown in Figure 4, first charge-discharge efficiency: 85.3%.First discharge specific capacity: 886mAh/g (with the Mass Calculation of copper silicon compound, the copper-clad herein in copper silicon compound draws together the copper that welding compound enters).
Embodiment 5
The preparation of copper silicon compound active material: be that copper source (31g) is dissolved in the mixed solution of absolute ethyl alcohol and deionized water by copper acetate, taking silicon (6g) joins in the mixed solution of copper acetate, is finally joined in above-mentioned mixed solution as surfactant by the polyacrylic acid aqueous solution (75g).Carry out spraying dry to the mixed solution configured and prepare composite material, spraying dry selects nitrogen atmosphere, and temperature is 160 DEG C, then will prepare composite material keep under an atmosphere of hydrogen 500 DEG C, 6h occur reduction reaction prepare copper silicon compound.
Prepared by metallic compound cupric oxide: the ammonia spirit taking 40g Schweinfurt green or copper organic acid salting liquid, water, 31g, by even for above-mentioned aqueous solution, the suspension solution mixed is carried out spraying dry at 180 DEG C, in air, prepares Cu (OH)
2powder, by Cu (OH)
2powder, at 200 DEG C, keeps 6h to prepare CuO, Cu
2o powder.
The preparation of copper silicon compound pole piece: blended anode material copper silicon compound (0.4g), metallic compound cupric oxide (0.05g), the bonding reducing agent PAA aqueous solution (0.3g), deionized water prepare slurry, and slurry is applied to collector Cu paper tinsel surface to be prepared pole piece and dries.
Pole piece welds: carry out 2MPa/cm to above-mentioned pole piece
2be positioned over after precompressed (nitrogen atmosphere) in tube furnace, keep 6h to carry out welding pole piece is welded successfully at 500 DEG C.Final pressure compacting (1MPa/cm is carried out to pole piece after welding
2) after prepare diameter 14mm disk for assembling button cell (negative pole selects lithium sheet).Button cell test result: first charge-discharge efficiency: 53.1%, first discharge specific capacity: 564mAh/g (with the Mass Calculation of copper silicon compound, the copper-clad herein in copper silicon compound draws together the copper that welding compound enters).、
Embodiment 6
Take silicon 0.2g, cupric oxide 1g, Aqueous Solutions of Polyethylene Glycol 3g prepares uniform slurry, a coated copper foil surface preparation pole piece, carries out 1MPa/cm to a pole piece
2after precompressed process, 500 DEG C of maintenance 6h weld under nitrogen atmosphere, and pole piece keeps 2h 300 DEG C of atmosphere of hydrogen afterwards.
Prepare button cell to carrying out diameter 14mm cutting with superior pole piece, cell testing results is as follows: as shown in Figure 5, first charge-discharge efficiency: 46.3%.First discharge specific capacity: 476mAh/g (with the Mass Calculation of copper silicon compound, the copper-clad herein in copper silicon compound draws together the copper that welding compound enters).
Embodiment 7
With embodiment 1, unlike, institute's surfactant is the aqueous solution of polymethyl acrylate; Described in the preparation of described copper silicon compound active material, copper source is copper nitrate, copper acetate and acetylacetone copper; In the preparation of described copper silicon compound active material, the temperature of reduction reaction is 400 DEG C; In described pole piece welding, welding temperature is 600 DEG C, and weld time is 4 hours; Described spray drying temperature is 180 DEG C; The pressure of described pole piece precompressed is 10MPa/cm
2; The pressure of described pole piece final pressure compacting is 5MPa/cm
2.The pole piece of preparation is cut into the disk that diameter is 14mm, for assembling button cell (lithium sheet is done electrode).First charge-discharge efficiency: 80.1%.First discharge specific capacity: 955mAh/g (Mass Calculation with copper silicon compound).
Embodiment 8
With embodiment 1, unlike, institute's surfactant is polyethylene glycol and the polyacrylic aqueous solution; Described in the preparation of described copper silicon compound active material, copper source is copper nitrate and copper chloride; Described in the preparation of described copper silicon compound pole piece, collector is foam copper; In the preparation of described copper silicon compound active material, the temperature of reduction reaction is 600 DEG C; In described pole piece welding, welding temperature is 700 DEG C, and weld time is 2 hours; Described spray drying temperature is 140 DEG C; The pressure of described pole piece precompressed is 1MPa/cm
2; The pressure of described pole piece final pressure compacting is 10MPa/cm
2.The pole piece of preparation is cut into the disk that diameter is 14mm, for assembling button cell (lithium sheet is done electrode).First charge-discharge efficiency is 83.57%.First discharge specific capacity is 934mAh/g (Mass Calculation with copper silicon compound).
Embodiment 9
With embodiment 1, unlike, described in the preparation of described copper silicon compound active material, copper source is copper sulphate and Schweinfurt green; Described in the preparation of described copper silicon compound pole piece, collector is foam copper; In the preparation of described copper silicon compound active material, the temperature of reduction reaction is 400 DEG C; In described pole piece welding, welding temperature is 700 DEG C; Described spray drying temperature is 120 DEG C; The pressure of described pole piece precompressed is 1MPa/cm
2; The pressure of described pole piece final pressure compacting is 15MPa/cm
2.The pole piece of preparation is cut into the disk that diameter is 14mm, for assembling button cell (lithium sheet is done electrode).This button cell first charge-discharge efficiency is 86.57%.First discharge specific capacity is 964mAh/g (Mass Calculation with copper silicon compound).
Claims (44)
1. a copper silicium cathode, comprises negative active core-shell material and collector, it is characterized in that: described negative active core-shell material is siliceous, described negative active core-shell material by metal solder on collector.
2. copper silicium cathode as claimed in claim 1, is characterized in that: described negative active core-shell material is silicon or copper silicon compound.
3. copper silicium cathode as claimed in claim 2, is characterized in that: in described copper silicon compound, the content of silicon is 5wt% ~ 80wt%.
4. copper silicium cathode as claimed in claim 3, is characterized in that: in described copper silicon compound, the content of silicon is 10wt% ~ 60wt%.
5. copper silicium cathode as claimed in claim 3, is characterized in that: in described copper silicon compound, the content of silicon is 20wt% ~ 40wt%.
6. copper silicium cathode as claimed in claim 2, is characterized in that: described copper silicon compound is prepared from by silicon and mantoquita.
7. copper silicium cathode as claimed in claim 6, is characterized in that: described mantoquita is at least one in copper sulphate, Schweinfurt green, copper nitrate, acetylacetone copper and copper chloride; Described mantoquita can water-soluble and/or ethanol.
8. copper silicium cathode as claimed in claim 1, is characterized in that: described metal is metallic copper.
9. copper silicium cathode as claimed in claim 8, is characterized in that: described metallic copper is formed by reducing substances reduction copper compound.
10. copper silicium cathode as claimed in claim 9, is characterized in that: described reducing substances is reducing atmosphere and/or bonding reducing agent; Described bonding reducing agent is the polymer containing C, H, O.
11. copper silicium cathodes as claimed in claim 9, is characterized in that: described copper compound is at least one in cupric oxide, cuprous oxide, Kocide SD, copper nitrate and Schweinfurt green.
12. copper silicium cathodes as claimed in claim 1, is characterized in that: the particle diameter of described silicon is less than 5 μm.
13., as the copper silicium cathode of claim 12, is characterized in that: the particle diameter of described silicon is less than 1 μm.
14. copper silicium cathodes as claimed in claim 1, is characterized in that: described collector is Copper Foil or foam copper.
15. as described in any one of claim 1 to 14 preparation method of copper silicium cathode, comprise the following steps:
A, a pole piece preparation: copper silicon compound, bonding reducing agent, solvent form slurry are coated an obtained pole piece on collector;
Prepared by b, copper silicium cathode: be positioned in inert atmosphere by an above-mentioned pole piece and carry out reduction welding, namely obtain described copper silicium cathode after welding terminates.
The preparation method of 16. copper silicium cathodes as claimed in claim 13, is characterized in that: also comprise copper compound or copper powder in described slurry.
The preparation method of 17. copper silicium cathodes as claimed in claim 14, is characterized in that: the quality bonding reducing agent described in a pole piece preparation is 5% ~ 30% of the gross mass of copper compound and copper silicon compound.
The preparation method of 18. copper silicium cathodes as claimed in claim 14, is characterized in that: pass into reducing atmosphere during reduction welding in the preparation of copper silicium cathode.
The preparation method of 19. copper silicium cathodes as claimed in claim 13, is characterized in that: in the preparation of copper silicium cathode, welding temperature is 400 ~ 1000 DEG C; Weld time is 0.1 ~ 10 hour.
The preparation method of 20. copper silicium cathodes as claimed in claim 18, is characterized in that: in the preparation of copper silicium cathode, welding temperature is 500 ~ 900 DEG C; Weld time is 0.5 ~ 6 hour.
The preparation method of 21. copper silicium cathodes as claimed in claim 13, is characterized in that: in the preparation of copper silicium cathode, a pole piece carries out precompressed before putting into inert atmosphere; The pressure of described precompressed is 0.2 ~ 20MPa/cm
2.
The preparation method of 22. copper silicium cathodes as claimed in claim 13, is characterized in that: in the preparation of copper silicium cathode, welding carries out final pressure after terminating; The pressure of described final pressure is 0.2 ~ 20MPa/cm
2.
The preparation method of 23. copper silicium cathodes as claimed in claim 13, is characterized in that: bonding reducing agent described in a pole piece preparation is at least one in polyacrylic acid, polyethylene glycol and acrylic resin.
The preparation method of 24. copper silicium cathodes as claimed in claim 13, is characterized in that: the preparation method of described copper silicon compound comprises the following steps:
(1), a preparation copper silicon compound: mantoquita, silicon, surfactant and solvent are configured to suspension-turbid liquid, then the obtained copper silicon compound of suspension-turbid liquid described in spraying dry;
(2) copper silicon compound, is prepared: obtain described copper silicon compound with the above-mentioned copper silicon compound of reducing agent reduction.
The preparation method of 25. copper silicium cathodes as claimed in claim 23, is characterized in that: described in a copper silicon compound preparation, solvent is at least one in water, methyl alcohol and ethanol.
The preparation method of 26. copper silicium cathodes as claimed in claim 23, is characterized in that: described in a pole piece preparation, solvent is at least one in water, methyl alcohol and ethanol.
The preparation method of 27. copper silicium cathodes as claimed in claim 23, is characterized in that: described in the preparation of copper silicon compound, reducing agent is at least one in carbon, hydrogen, carbon monoxide, methane, ethane, propane, methyl alcohol, ethanol and acetone.
The preparation method of 28. copper silicium cathodes as claimed in claim 23, is characterized in that: described in a copper silicon compound preparation, the quality of surfactant is 0% ~ 225% of copper quality in copper silicon compound.
The preparation method of 29. copper silicium cathodes as claimed in claim 23, is characterized in that: surfactant described in a copper silicon compound preparation is the polymer containing C, H, O.
The preparation method of 30. copper silicium cathodes as claimed in claim 28, is characterized in that: described in a copper silicon compound preparation, surfactant is at least one in polyacrylic acid, polyethylene glycol and polymethyl acrylate.
The preparation method of 31. copper silicium cathodes as claimed in claim 29, is characterized in that: described in a copper silicon compound preparation, surfactant is polyacrylic acid.
The preparation method of 32. copper silicium cathodes as claimed in claim 23, is characterized in that: in a copper silicon compound preparation, spray-dired temperature is 100 DEG C ~ 200 DEG C.
The preparation method of 33. copper silicium cathodes as claimed in claim 23, is characterized in that: in the preparation of copper silicon compound, during reducing agent reduction, temperature controls to be 200 ~ 800 DEG C.
The preparation method of 34. copper silicium cathodes as claimed in claim 32, is characterized in that: in the preparation of copper silicon compound, during reducing agent reduction, temperature controls to be 250 ~ 500 DEG C.
35. as claim 1 to 2, and the preparation method of copper silicium cathode described in 8 to 14 any one, comprises the following steps:
A, pole piece preparation: by silica flour, bonding reducing agent, solvent, and copper compound or copper powder are mixed into slurry and coat an obtained pole piece on collector;
Prepared by b, copper silicium cathode: be positioned in inert atmosphere by an above-mentioned pole piece and carry out reduction welding, namely obtain described copper silicium cathode after welding terminates.
The preparation method of 36. copper silicium cathodes as claimed in claim 35, the quality bonding reducing agent described in a pole piece preparation is 5% ~ 50% of silicon and copper compound gross mass.
The preparation method of 37. copper silicium cathodes as claimed in claim 35, the quality bonding reducing agent described in a pole piece preparation is 5% ~ 50% of silicon and copper powder gross mass.
The preparation method of 38. copper silicium cathodes as claimed in claim 35, passes into reducing atmosphere during reduction welding in the preparation of copper silicium cathode.
The preparation method of 39. copper silicium cathodes as claimed in claim 35, is characterized in that: in the preparation of copper silicium cathode, welding temperature is 400 ~ 1000 DEG C; Weld time is 0.1 ~ 10 hour.
The preparation method of 40. copper silicium cathodes as claimed in claim 39, is characterized in that: in the preparation of copper silicium cathode, welding temperature is 500 ~ 900 DEG C; Weld time is 0.5 ~ 6 hour.
The preparation method of 41. copper silicium cathodes as claimed in claim 35, is characterized in that: in the preparation of copper silicium cathode, a pole piece carries out precompressed before putting into inert atmosphere; The pressure of described precompressed is 0.2 ~ 20MPa/cm
2.
The preparation method of 42. copper silicium cathodes as claimed in claim 35, is characterized in that: in the preparation of copper silicium cathode, welding carries out final pressure after terminating; The pressure of described final pressure is 0.2 ~ 20MPa/cm
2.
The preparation method of 43. copper silicium cathodes as claimed in claim 35, is characterized in that: bonding reducing agent described in a pole piece preparation is at least one in polyacrylic acid, polyethylene glycol and acrylic resin.
44. 1 kinds of lithium ion batteries, comprise the copper silicium cathode as described in any one of claim 1 to 14.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017190587A1 (en) * | 2016-05-02 | 2017-11-09 | 北京工业大学 | Method for preparing lithium ion battery silicon anode through combination of diffusion welding and dealloying with laser surface remelting technique |
| CN107394150A (en) * | 2017-07-14 | 2017-11-24 | 东南大学 | A kind of mesoporous silicon copper composition electrode material and its preparation method and application |
| CN108335800A (en) * | 2017-12-29 | 2018-07-27 | 天津工业大学 | Copper silicon integrated electrode and preparation method thereof |
| CN108550801A (en) * | 2018-02-11 | 2018-09-18 | 合肥国轩高科动力能源有限公司 | A kind of silicon/copper/fibrous carbon/carbide composite material and preparation, application |
| CN108807888A (en) * | 2018-05-24 | 2018-11-13 | 天津工业大学 | A kind of three-dimensional porous copper silicon-carbon composite integrated polarizing electrode and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1595683A (en) * | 2003-09-10 | 2005-03-16 | 中国科学院物理研究所 | Nanometer metal or alloy composite material and preparation and usage thereof |
| CN101425572A (en) * | 2007-10-29 | 2009-05-06 | 比亚迪股份有限公司 | Anode plate for lithium ionic cell and preparation thereof |
| CN102208617A (en) * | 2010-03-31 | 2011-10-05 | 比亚迪股份有限公司 | Method for preparing cathode active substance of lithium ion secondary cells |
| CN102484241A (en) * | 2009-03-03 | 2012-05-30 | 尤米科尔公司 | Process for preparing alloy composite negative electrode material for lithium ion batteries |
-
2014
- 2014-09-18 CN CN201410475617.9A patent/CN105489839A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1595683A (en) * | 2003-09-10 | 2005-03-16 | 中国科学院物理研究所 | Nanometer metal or alloy composite material and preparation and usage thereof |
| CN101425572A (en) * | 2007-10-29 | 2009-05-06 | 比亚迪股份有限公司 | Anode plate for lithium ionic cell and preparation thereof |
| CN102484241A (en) * | 2009-03-03 | 2012-05-30 | 尤米科尔公司 | Process for preparing alloy composite negative electrode material for lithium ion batteries |
| CN102208617A (en) * | 2010-03-31 | 2011-10-05 | 比亚迪股份有限公司 | Method for preparing cathode active substance of lithium ion secondary cells |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017190587A1 (en) * | 2016-05-02 | 2017-11-09 | 北京工业大学 | Method for preparing lithium ion battery silicon anode through combination of diffusion welding and dealloying with laser surface remelting technique |
| CN107394150A (en) * | 2017-07-14 | 2017-11-24 | 东南大学 | A kind of mesoporous silicon copper composition electrode material and its preparation method and application |
| CN108335800A (en) * | 2017-12-29 | 2018-07-27 | 天津工业大学 | Copper silicon integrated electrode and preparation method thereof |
| CN108335800B (en) * | 2017-12-29 | 2020-12-11 | 天津工业大学 | Copper-silicon integrated electrode and preparation method thereof |
| CN108550801A (en) * | 2018-02-11 | 2018-09-18 | 合肥国轩高科动力能源有限公司 | A kind of silicon/copper/fibrous carbon/carbide composite material and preparation, application |
| CN108807888A (en) * | 2018-05-24 | 2018-11-13 | 天津工业大学 | A kind of three-dimensional porous copper silicon-carbon composite integrated polarizing electrode and preparation method thereof |
| CN108807888B (en) * | 2018-05-24 | 2021-05-18 | 天津工业大学 | Three-dimensional porous copper silicon carbon composite integrated electrode and preparation method thereof |
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