CN104009208A - Method for synthesizing nanometer Ni2O3/Co3O4 cathode material on copper sheet current collector through two-step method - Google Patents
Method for synthesizing nanometer Ni2O3/Co3O4 cathode material on copper sheet current collector through two-step method Download PDFInfo
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- B82Y40/00—Manufacture or treatment of nanostructures
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for synthesizing a nanometer Ni2O3/Co3O4 cathode material on a copper sheet current collector through a two-step method. According to the method, a nanowire array directly grows on the current current collector matrix, so that the process treatment is greatly simplified, and an adhesive and a conductive additive are not used in the electrode. The method comprises the following steps: electroplating a nano-scale granular nickel layer on a copper matrix subjected to acid treatment to serve as a seed, generating a nano array through a hydrothermal reaction, and preparing a final product through high-temperature calcining. The proper nickel electroplating time is selected, the combination degree between the substrate and the material is improved, and the nickel is hard to drop, so that the cycling stability of the lithium ion battery is improved. Meanwhile, compared with a nickel plating-free pure Co3O4 array, the Ni2O3/Co3O4 array has the advantages that the capacity value of unit area is improved. When the electrochemical performance is tested, the prepared cathode material reflects high charging and discharging capacity and long cycle life.
Description
Technical field
The present invention relates to one two step synthesis nanometer Ni on copper sheet collector
2o
3/ Co
3o
4the method of negative material, particularly a kind of method of preparing negative electrode for lithium ion battery material by plating and hydro-thermal two-step synthetic method.
Background technology
Along with economical and social development, the fossil energies such as oil, coal reduce day by day, and energy security problem has become the key subjects of human survival and development, and the green regenerative energy sources of development of new is the effective ways that solve energy shortage problem.In recent years, along with the technology upgrading of various middle-size and small-size portable type electronic products, and the exploitation of New Generation of Electric Vehicle/hybrid vehicle and business promotion, the energy density to battery and performance propose higher requirement.Theory and practice proves, the advantage such as lithium rechargeable battery has that specific energy is high, operating voltage is high, has extended cycle life, safety non-pollution, has become with fastest developing speed and the most valued high-performance secondary cell.
Make and obtain lithium ion battery success excellent properties, can key be prepare the reversibly negative material of removal lithium embedded ion.In general, select a kind of good negative material should follow following principle: specific energy is high; The electrode potential of lithium electrode is low relatively; Discharge and recharge reaction good reversibility; Good with the compatibility of electrolyte and binding agent; Specific area is little, real density is high, size and good mechanical stability in embedding lithium process; Aboundresources, cheap; Stable in the air, have no side effect etc.The nanometer of lithium ion battery electrode material and structure function are thought the effective ways that address these problems, and the crystal structure of nano-electrode material, pattern and size etc. all have material impact to its chemical property simultaneously.With large-sized Particle Phase ratio, the particle of nano-scale has larger specific surface, more lithium ion admission passage is provided, and makes material structure more stable, thereby have better chemical property.Research shows, can improve material conductivity by methods such as nanometer and pattern controls, alleviates the volumetric expansion while charging, improves the chemical property of material.Therefore the nanometer and the functionalization that, how to realize lithium ion battery electrode material will be a research highly significant.
At present, the negative material that has been actually used in lithium ion battery is all carbon materials substantially, as electrographite etc.In the specific capacity of material with carbon element of research generally not higher than 400mAhg
-1, because irreversible loss is large first, multiplying power discharging property is poor etc., its assembled battery far away can not practical requirement.Lithium ion battery negative material is the key components of lithium ion battery, and therefore development of new height ratio capacity lithium ion battery negative material plays decisive action to further developing of lithium ion battery.
The Co of spinel structure
3o
4because it is easy to preparation, environmental friendliness, with low cost and relatively high theoretical specific capacity (892mAhg
-1) etc. advantage, be considered to a kind of lithium ion battery negative material of very potential and tool high safety performance.But due to Co
3o
4low electrical conductivity (tool semiconductor property) and the caused volumetric expansion of removal lithium embedded that utmost point material is intrinsic, cause in charge and discharge process capacity attenuation comparatively obvious, and particularly the stable circulation performance under large multiplying power is poor, has affected its extensive use.In order to improve its low problem such as conductibility and volumetric expansion, the present invention adopts the nano particle of direct plating one deck nickel on collector as seed, and then hydro-thermal reaction is synthesized Co thereon
3o
4nano-array, the electrochemistry inertia auxiliary material such as use conductive acetylene is black, binding agent are avoided, obtain that manufacture method is simple, electrical conductivity is high and compared with the electrode material of height ratio capacity, the application of nickel dam has improved the mechanical strength between nano-array and collector matrix, makes its electrochemistry cycle performance more stable.
Summary of the invention
The present invention adopts two-step synthetic method to prepare high performance lithium ion battery negative material first, two-step synthetic method is respectively to be electroplated and hydro thermal method, first directly on collector copper base, plate one deck nickel nano particle by galvanoplastic, thereafter Synthesized by Hydrothermal Method array structure on the copper matrix that is coated with nickel dam, this active material is directly created on to the method on collector, can economize the interpolation of no-bonder and conductive black etc., thereby improve the conductivity of material.The introducing of simultaneously suitable nickel nano particle can obviously improve the nano-array material of generation and the conjugation of copper matrix, impels active material difficult drop-off, improves the cyclical stability of material.Finally the composite material of synthetic metal oxide can effectively solve material volume expansion, and the shortcomings such as easy-weathering, have excellent chemical property.
One of the present invention is two step synthesis nanometer Ni on copper sheet collector
2o
3/ Co
3o
4the method of negative material, comprises the following steps:
(1) by polishing copper sheet through sour preliminary treatment, using the aqueous solution of nickelous sulfate, nickel chloride, boric acid and lauryl sodium sulfate as electroplate liquid, at certain temperature and mixing speed, generate the nickel of one deck nano-scale particle as seed.
(2) copper sheet after electronickelling is transferred to the autoclave inside liner of the mixed aqueous solution of cobalt nitrate, urea and ammonium fluoride, heating reactor, and constant temperature a period of time, be cooled to room temperature subsequently, after washing is dry nano thread structure array.
(3) product of step (2) is made to Ni through high-temperature calcination
2o
3/ Co
3o
4nano composite material.
According to above-mentioned preparation method, described in step (1), be wherein by 200-400g/L nickelous sulfate, 20-50g/L nickel chloride, 30-50g/L boric acid, 0.1-0.5g/L lauryl sodium sulfate is dissolved in distilled water as electroplate liquid after mixing.
According to above-mentioned preparation method, what wherein in step (1), use is the copper sheet through polishing, at the concentrated sulfuric acid, and preliminary treatment one minute under the nitration mixture of nitric acid and hydrochloric acid.
According to above-mentioned preparation method, in step (1), be wherein at magnetic agitation speed 500-800r/min, temperature is that at 40-50 DEG C, the method bipolar electrode with constant current is electroplated, copper sheet after treatment is as work electrode, pure nickel sheet, as to electrode, repeatedly washs the copper matrix that obtains nano nickel particles after plating.
According to above-mentioned preparation method, wherein in step (1), the time of electronickelling is 1s-50min.
According to above-mentioned preparation method, wherein step (2) is by 1.0-3.0g cobalt nitrate in described, and 0.3-0.5g ammonium fluoride and 1.0-3.0g urea are dissolved in 50mL distilled water, slowly stir about 30 minutes.
According to above-mentioned preparation method, wherein the copper sheet after the described middle electronickelling of step (2) is transferred in autoclave liner, put into reaction solution with miter angle, keep 1-5 hour at 120 DEG C of constant temperature, naturally cooling, wash respectively at least three times with ultra-pure water and ethanol, after sample is dry at 60 DEG C of air dry ovens, obtain nanowire array structure.
According to above-mentioned preparation method, wherein step (3) is described middlely at high temperature 350-450 DEG C calcines product 3 hours in Muffle furnace under air atmosphere, finally obtains product.
Good effect of the present invention is: adopt the good copper sheet of conductivity as substrate, save the interpolation of binding agent and conductive black etc., thereby improve the conductivity of material, the simultaneously introducing of suitable nickel nano particle can obviously improve the mechanical strength between nano-array material and the copper substrate of generation, strengthen adhesion impel nano-array and substrate more firm, difficult drop-off in the time of battery performance test, because metallic nickel after high-temperature calcination is oxidized to Ni in air
2o
3oxide, with the simple Co without nickel plating
3o
4array is compared, Ni
2o
3/ Co
3o
4array has improved the capability value of unit are.An obvious rule is found in regulation and control by the electronickelling time, and in the time that electroplating time is 10-40s, the conjugation between material is better, when the time is too short while being 1s left and right and the long 20-50min conjugation of electroplating time is all poor, easily comes off.And in order stable array structure is conducive to the embedding of lithium ion in charge and discharge process/deviate from, and therefore selects the material list of the generation after suitable electroplating time hydro-thermal to reveal good chemical property, high power capacity.
Brief description of the drawings
Fig. 1 is the scanning electron microscope diagram through the pretreated copper sheet of acid in case study on implementation 1, and the copper sheet of polishing becomes uneven through acid treatment rear surface as seen from the figure.
Fig. 2 is the scanning electron microscope diagram of copper sheet after 10s electronickelling after processing in case study on implementation 1, and the pattern that can obviously observe after nickel plating is nano particle.
Fig. 3 is the scanning electron microscope diagram after the copper sheet hydro-thermal reaction after electronickelling in case study on implementation 1 (10S), and the nano-array that shows showy flowers of herbaceous plants shape from figure generates.
Fig. 4 is the scanning electron microscope diagram after the copper sheet hydro-thermal reaction after electronickelling in case study on implementation 2 (10S);
Fig. 5 is the scanning electron microscope diagram after the copper sheet hydro-thermal reaction after electronickelling in case study on implementation 3 (10S);
Fig. 6 is the scanning electron microscope diagram after the copper sheet hydro-thermal reaction after electronickelling in case study on implementation 4 (30min), and observing surface has a large amount of cracks.
Fig. 7 is the scanning electron microscope diagram after the copper sheet hydro-thermal reaction after electronickelling in case study on implementation 5 (1s), shows that showy flowers of herbaceous plants shape nano-array distributes very sparse from figure.
Embodiment
The present invention illustrates by following examples, but following examples only tool is illustrative, before and after not departing from, under the scope of described aim, change is included in technical scope of the present invention.
In battery performance test result, find nanometer Ni
2o
3/ Co
3o
4negative material is than the Co that is grown directly upon copper sheet
3o
4negative material is compared has higher specific volume value and good cycle performance.
Embodiment 1
The fine copper sheet of polishing is cut into size 1 × 3cm, the lower preliminary treatment of nitration mixture (concentrated sulfuric acid, nitric acid, hydrochloric acid) a minute.250g/L nickelous sulfate, 30g/L nickel chloride, 35g/L boric acid, 0.1g/L lauryl sodium sulfate is dissolved in distilled water as electroplate liquid after mixing, at magnetic agitation speed 700r/min, temperature is that at 45 DEG C, the method bipolar electrode with constant current is electroplated, and current density is at 0.75A/dm
3under, electroplating time is 10s, and copper sheet after treatment is as work electrode, and pure nickel sheet, as to electrode, repeatedly washs after plating and dries up through nitrogen.Then by 1.46g cobalt nitrate, 0.37g ammonium fluoride and 1.5g urea are dissolved in 50mL distilled water, slowly stir about 30 minutes, then getting 35ml solution is transferred in autoclave liner, copper sheet after electronickelling 45 is spent to angle of inclination and put into reaction solution, keep 5 hours at 120 DEG C of constant temperature, naturally cooling, wash respectively at least three times sample at 60 DEG C of air dry ovens dry 12 hours with ultra-pure water and ethanol.In Muffle furnace, under air atmosphere, at 450 DEG C of high temperature, calcine 3 hours, finally obtain product.From Fig. 2 scanning electron microscope diagram, find out after nickel plating to be Nanoparticulate structure, show regular showy flowers of herbaceous plants shape nano-wire array from Fig. 3 scanning electron microscope diagram, show through X-ray diffraction and XPS analysis, nano-wire array is Co
3o
4.After high-temperature calcination, nickel particles is oxidized to Ni
2o
3oxide.
Embodiment 2
The fine copper sheet of polishing is cut into size 1 × 3cm, the lower preliminary treatment of nitration mixture (concentrated sulfuric acid, nitric acid, hydrochloric acid) a minute.250g/L nickelous sulfate, 30g/L nickel chloride, 35g/L boric acid, 0.1g/L lauryl sodium sulfate is dissolved in distilled water as electroplate liquid after mixing, at magnetic agitation speed 700r/min, temperature is that at 45 DEG C, the method bipolar electrode with constant current is electroplated, and current density is at 0.75A/dm
3under, electroplating time is 10s, and copper sheet after treatment is as work electrode, and pure nickel sheet, as to electrode, repeatedly washs after plating and dries up through nitrogen.Then by 1.46g cobalt nitrate, 0.37g ammonium fluoride and 1.5g urea are dissolved in 50mL distilled water, slowly stir about 30 minutes, then getting 35ml solution is transferred in autoclave liner, copper sheet after electronickelling 45 is spent to angle of inclination and put into reaction solution, different from example 1 is to keep 1 hour at 120 DEG C of constant temperature, naturally cools to room temperature, wash respectively at least three times sample at 60 DEG C of air dry ovens dry 12 hours with ultra-pure water and ethanol.In Muffle furnace, under air atmosphere, at 450 DEG C of high temperature, calcine 3 hours, finally obtain product.Show the orthotropic nano-array of rule from Fig. 4 scanning electron microscope diagram.
Embodiment 3
The fine copper sheet of polishing is cut into size 1 × 3cm, the lower preliminary treatment of nitration mixture (concentrated sulfuric acid, nitric acid, hydrochloric acid) a minute.250g/L nickelous sulfate, 30g/L nickel chloride, 35g/L boric acid, 0.1g/L lauryl sodium sulfate is dissolved in distilled water as electroplate liquid after mixing, at magnetic agitation speed 700r/min, temperature is that at 45 DEG C, the method bipolar electrode with constant current is electroplated, and current density is at 0.75A/dm
3under, electroplating time is 10s, and copper sheet after treatment is as work electrode, and pure nickel sheet, as to electrode, repeatedly washs after plating and dries up through nitrogen.Then by 1.46g cobalt nitrate, 0.37g ammonium fluoride and 0.15g urea are dissolved in 50mL distilled water, slowly stir about 30 minutes, then getting 35ml solution is transferred in autoclave liner, copper sheet after electronickelling 45 is spent to angle of inclination and put into reaction solution, keep 5 hours at 120 DEG C of constant temperature, naturally cool to room temperature, wash respectively at least three times sample at 60 DEG C of air dry ovens dry 12 hours with ultra-pure water and ethanol.In Muffle furnace, under air atmosphere, at 450 DEG C of high temperature, calcine 3 hours.From Fig. 5 scanning electron microscope diagram find out product pattern because of urea content reduce change, do not have array generate.
Embodiment 4
The fine copper sheet of polishing is cut into size 1 × 3cm, the lower preliminary treatment of nitration mixture (concentrated sulfuric acid, nitric acid, hydrochloric acid) a minute.250g/L nickelous sulfate, 30g/L nickel chloride, 35g/L boric acid, 0.1g/L lauryl sodium sulfate is dissolved in distilled water as electroplate liquid after mixing, at magnetic agitation speed 700r/min, temperature is that at 45 DEG C, the method bipolar electrode with constant current is electroplated, and current density is at 0.75A/dm
3under, electroplating time changes into as 40min, and copper sheet after treatment is as work electrode, and pure nickel sheet, as to electrode, repeatedly washs after plating and dries up through nitrogen.Then by 1.46g cobalt nitrate, 0.37g ammonium fluoride and 1.5g urea are dissolved in 50mL distilled water, slowly stir about 30 minutes, then getting 35ml solution is transferred in autoclave liner, copper sheet after electronickelling 45 is spent to angle of inclination and put into reaction solution, keep 5 hours at 120 DEG C of constant temperature, naturally cooling, wash respectively at least three times sample at 60 DEG C of air dry ovens dry 12 hours with ultra-pure water and ethanol.In Muffle furnace, under air atmosphere, at 450 DEG C of high temperature, calcine 3 hours.Find the raising along with electroplating time from Fig. 6 scanning electron microscope diagram, surface produces a large amount of cracks.
Embodiment 5
The fine copper sheet of polishing is cut into size 1 × 3cm, the lower preliminary treatment of nitration mixture (concentrated sulfuric acid, nitric acid, hydrochloric acid) a minute.250g/L nickelous sulfate, 30g/L nickel chloride, 35g/L boric acid, 0.1g/L lauryl sodium sulfate is dissolved in distilled water as electroplate liquid after mixing, at magnetic agitation speed 700r/min, temperature is that at 45 DEG C, the method bipolar electrode with constant current is electroplated, and current density is at 0.75A/dm
3under, electroplating time changes into as 1s, and next step hydro-thermal reaction keeps 5 hours at 120 DEG C of constant temperature, naturally cools to room temperature, then at 450 DEG C of high temperature, calcines 3 hours.Find out that from Fig. 7 scanning electron microscope diagram to cause careless flower-like structure very sparse due to plating time very short-range missile, cause the quality of unit are active material to reduce.
Claims (8)
1. a two step synthesis nanometer Ni on copper sheet collector
2o
3/ Co
3o
4the method of negative material, comprises the following steps:
(1) by polishing copper sheet through sour preliminary treatment, using the aqueous solution of nickelous sulfate, nickel chloride, boric acid and lauryl sodium sulfate as electroplate liquid, at certain temperature and mixing speed, generate the nickel of one deck nano-scale particle as seed;
(2) copper sheet after electronickelling is transferred to the autoclave inside liner of the mixed aqueous solution of cobalt nitrate, urea and ammonium fluoride, heating reactor, and constant temperature a period of time, be cooled to room temperature subsequently, after washing is dry nano thread structure array;
(3) product of step (2) is made to Ni through high-temperature calcination
2o
3/ Co
3o
4nano composite material.
2. preparation method according to claim 1, it is characterized in that: described in step (1), be by 200-400g/L nickelous sulfate, 20-50g/L nickel chloride, 30-50g/L boric acid, 0.1-0.5g/L lauryl sodium sulfate is dissolved in distilled water as electroplate liquid after mixing.
3. preparation method according to claim 1, is characterized in that: what in step (1), use is the copper sheet through polishing, at the concentrated sulfuric acid, and preliminary treatment one minute under the nitration mixture of nitric acid and hydrochloric acid.
4. preparation method according to claim 1, it is characterized in that: in step (1), be at magnetic agitation speed 500-800r/min, temperature is that at 40-50 DEG C, the method bipolar electrode with constant current is electroplated, copper sheet after treatment is as work electrode, pure nickel sheet, as to electrode, repeatedly washs the copper matrix that obtains nano nickel particles after plating.
5. preparation method according to claim 1, is characterized in that: in step (1), the time of electronickelling is 1s-50min.
6. preparation method according to claim 1, is characterized in that: in step (2), be by 1.0-3.0g cobalt nitrate, 0.3-0.5g ammonium fluoride and 1.0-3.0g urea are dissolved in 50mL distilled water, slowly stir about 30 minutes.
7. preparation method according to claim 1, it is characterized in that: the copper sheet in step (2) after electronickelling is transferred in autoclave liner, put into reaction solution with miter angle, keep 1-5 hour at 120 DEG C of constant temperature, naturally cooling, wash respectively at least three times with ultra-pure water and ethanol, after sample is dry at 60 DEG C of air dry ovens, obtain nanowire array structure.
8. preparation method according to claim 1, is characterized in that: step (3) is described middlely at high temperature 350-450 DEG C calcines product 3 hours in Muffle furnace under air atmosphere, finally obtains product.
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