CN109873117B - Electrode for lithium ion battery and preparation and application thereof - Google Patents
Electrode for lithium ion battery and preparation and application thereof Download PDFInfo
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- CN109873117B CN109873117B CN201711246821.3A CN201711246821A CN109873117B CN 109873117 B CN109873117 B CN 109873117B CN 201711246821 A CN201711246821 A CN 201711246821A CN 109873117 B CN109873117 B CN 109873117B
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Abstract
The invention discloses an electrode for a lithium ion battery and preparation and application thereof, wherein a foamed nickel plate is used as a catalyst of the electrode, the foamed nickel plate is contacted with the outer surface of a platy silicon electrode matrix on which a conductive substance is to be deposited, a contact chemical plating process is adopted to realize chemical in-situ deposition on the silicon electrode matrix, and a nickel-phosphorus composite coating is deposited on the surface and inside of the silicon electrode matrix.
Description
Technical Field
The invention relates to silicon negative electrode preparation in secondary lithium ion batteries.
Background
In recent years, with the increasing global energy environment crisis, the lithium ion battery has the advantages of no memory effect, rapid reversible charge and discharge, high coulombic efficiency and the like, and has become the preferred power source for various electronic products such as notebook computers, electric bicycles and other electronic devices.
However, the research of the large-capacity lithium ion battery is slow. This is because lithium cobaltate, lithium manganate, lithium iron phosphate and their derivatives, which are currently used as positive electrode materials for lithium ion batteries, and commercially available negative electrode material graphite are close to theoretical capacities and are difficult to be improved. In order to meet the demand for high-capacity lithium ion secondary batteries, a new electrode material with high capacity and low cost has become a research focus in recent years.
Compared with the traditional graphite negative electrode material, the specific capacity of the silicon material (4200mAh g)-1) Is more than ten times of natural graphite. Compared with metal lithium, the bulk density of silicon in the alloy material is similar to that of lithium, so that the silicon also has very high volume specific capacity, and the high specific capacity of the silicon is derived from the alloying process of silicon and lithium, so that the silicon negative electrode material cannot be subjected to solvent co-intercalation with electrolyte, and the trial range of the electrolyte is wider; compared with a carbon material, silicon has higher lithium-releasing and-inserting potential, can effectively avoid the precipitation of lithium in the process of high-rate charge and discharge, and can improve the safety of the battery.
Due to the influence of a volume effect (the expansion rate is about 300%), a silicon electrode is structurally damaged in the charging and discharging process, so that an active material is peeled off from a current collector, electric contact between the active material and between the active material and the current collector is lost, and meanwhile, a new solid electrolyte layer (SEI) is continuously formed, so that the silicon electrode negative electrode material cannot exert better battery performance in the aspects of reversible capacity, cycle stability and rate performance. The existing solution strategies comprise nanocrystallization, compositing and the like of silicon-based materials, and the buffer matrix used for compositing has small volume effect and good conductivity, can inhibit the volume change of silicon in the charging and discharging processes, enhances the contact tightness of the silicon and a conductive framework, and can be simply divided into two types of silicon-metal composite cathode materials and silicon-nonmetal composite electrode materials. However, as the charging and discharging processes proceed, the electrode still has irreversible volume change and cannot be restored during the charging and discharging processes, and finally, the capacity is gradually attenuated due to the destruction of the electrode structure.
The chemical plating is used as an autocatalytic deposition reaction technology, and the coating deposited by the method has the characteristics of uniform thickness, high deposition speed and the like. The problems of current collection and conductivity of the flexible electrode can be well solved by carrying out chemical plating deposition on the flexible electrode material by the existing chemical plating method. If the technology can be used for three-dimensionally depositing the coating with high conductivity and high elasticity on the silicon cathode material, the conductivity problem of the electrode material can be improved, and meanwhile, the structure and the appearance of the electrode material can be well maintained through the deposition of the high-elasticity coating, so that the better battery performance is maintained. Therefore, the development of the silicon cathode material deposited by the three-dimensional high-elasticity and high-conductivity chemical plating composite coating for the lithium ion battery is very significant.
The invention content is as follows:
the invention provides a method for preparing a high-elasticity and high-conductivity nickel-phosphorus composite coating on the surface and in the interior of a silicon negative electrode material by adopting foamed nickel as a contact catalyst and realizing the chemical plating deposition of the nickel-phosphorus composite coating on the silicon negative electrode material through the close contact with an electrode material.
The electrode takes foamed nickel as a catalyst, a foamed nickel plate is contacted with the outer surface of a plate-shaped silicon electrode substrate on which a conductive substance is to be deposited, the chemical in-situ deposition of the silicon electrode substrate is realized by adopting a contact chemical plating process, so that a nickel-phosphorus composite coating is deposited on the surface and the inside of the silicon electrode substrate, and the thickness of a metal coating on the surface of the electrode is 0.3-3 mu m; the silicon electrode substrate comprises an active substance, a conductive carbon material, a binder or the active substance and the binder; wherein the mass content of the active substance is 60-80%, the mass content of the conductive carbon material is 0-20%, the mass content of the binder is 10-35%, and the mass content of the nickel-phosphorus composite coating on the surface layer and inside the electrode matrix accounts for 1-10wt% of the electrode.
The conductive carbon material comprises one or more than two of carbon nano tubes, graphene, carbon nano fibers, KB600, KB300 and Super-P.
The binder is one or more of polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyvinylidene fluoride (PVDF), and polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP).
The active material is one or two of silicon oxide, nano silicon particles, porous silicon, silicon/metal and silicon/carbon composite materials.
The preparation method of the electrode comprises the following steps of,
1) foam nickel pretreatment: putting the foamed nickel into an aqueous solution of sulfuric acid, hydrochloric acid or nitric acid with the pH value of 2.0-5.0 for 5-20 minutes, and then washing the foamed nickel by deionized water;
2) stacking the pretreated foamed nickel and the electrode surface and the surface opposite layer prepared by the plate-shaped electrode substrate of claims 1-4 together, fixing the laminated nickel by using a clamp or a rubber band to ensure that the surface and the surface are in close contact, and placing the laminated nickel in chemical plating solution;
3) carrying out chemical plating Ni-P composite coating modification on an electrode material: the chemical plating solution comprises an aqueous solution consisting of nickel salt, a compound solution, a reducing agent, a complexing agent and a buffering agent; the nickel salt is one or more of nickel chloride, nickel sulfate, nickel phosphate and nickel acetate, and the final concentration is 10-50 g/L; the composite solution comprises one or more than two of PTFE and PVDF aqueous solutions, and 1-7ml of 10wt% PTFE aqueous solution and/or 10wt% PVDF aqueous solution can be put into each liter of plating solution; the reducing agent is sodium hypophosphite with the final mass concentration of 10-50 g/L; the complexing agent is one or more than two of EDTA, EGTA, sodium tartrate and sodium citrate, and the final mass concentration is 10-50 g/L; the buffer is one or more than two of sodium acetate, ammonium acetate and ammonium chloride, and the final mass concentration is 10-50 g/L; the nickel salt in the electroless plating solution is preferably nickel phosphate. The pH value of the plating solution is between 4.0 and 5.0 or between 8.0 and 9.5; the temperature is controlled between 60 ℃ and 90 ℃ and the time is controlled between 15 minutes and 8 hours in the chemical plating process.
The chemical plating solution also comprises a stabilizer which is one or more than two of sodium thiosulfate, potassium iodide and thiourea, and the final mass concentration is 0.01-0.1 g/L.
The pH regulator is adopted to regulate the pH of the plating solution, and the pH regulator is 100-400g/L hydrochloric acid or sulfuric acid solution; 40-160g/L sodium hydroxide or ammonia solution.
The electrode is used as a negative electrode and applied to a secondary lithium ion battery, and the secondary battery consists of a positive electrode, a membrane and a negative electrode.
The beneficial results of the invention are:
the invention deposits high-conductivity and high-elasticity metal nickel-phosphorus composite coating on the surface layer and the interior of the silicon negative electrode material by adopting the chemical plating technology, and realizes the control of the indexes of the components, the thickness, the appearance and the like of the material coated on the surface and the interior of the electrode material by adjusting the chemical plating time, the chemical plating solution components and the pH value. The surface energy, the conductivity and other parameters of the chemical plating coating are regulated and controlled, the utilization rate of active substances is improved, and the original structure and appearance of the battery are maintained, so that the cycle performance of the silicon cathode lithium ion battery is improved.
The electrode carries out in-situ deposition on the silicon-based negative electrode material by applying a contact chemical plating process, so that a nickel-phosphorus composite coating with high elasticity and high conductivity is deposited on the surface and inside of the electrode, the problem of capacity attenuation caused by the fact that the whole structure of the electrode is damaged by the stripping of an active substance due to the volume effect (the expansion rate is about 300%) of the silicon electrode in the process of lithium extraction and intercalation can be well inhibited, the current collection effect of the electrode and the electron transmission efficiency inside the electrode can be improved, the higher utilization rate of the active substance is realized, and the thickness of the deposited coating on the surface of the electrode is 0.3-3 mu m; the silicon negative electrode is applied to a lithium ion secondary battery, can obviously improve the performance and the energy density of the lithium ion battery negative electrode, and has great potential for realizing future industrial mass production.
Drawings
FIG. 1: comparison graph of front and rear electrodes of electroless Ni-P-PTFE
FIG. 2: rate performance discharge curves at 0.1C-1C rate for the assembled button cells of comparative example 1, and example 2;
FIG. 3: cycling stability testing of the assembled button cells of comparative example 1, example 1 and example 2;
FIG. 4: ac impedance testing of the silicon negative electrodes of comparative example 1, example 1 and example 2.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
Comparative example 1 (silicon negative electrode of Ni-P-PTFE without electroless deposition)
Dissolving 0.4g of binder PVDF in 12g of N-methylpyrrolidone (NMP), stirring for 1h, adding 1.2g of commercial nano silicon powder and 0.4g of super P conductive carbon powder, stirring for 4h, adjusting a scraper to 300 mu m, coating the mixture on a copper foil to form a film, drying the film at 65 ℃ overnight, shearing the film into small round pieces with the diameter of 10mm, weighing the small round pieces, drying the small round pieces in vacuum at 60 ℃ for 24h, and taking the small round pieces coated with the nano silicon particles as anodes (1.4mg cm) after the small round pieces are cut into small round pieces with the diameter of 10mm-2) Lithium sheet as negative electrode, celgard 2325 as diaphragm, 1M LiPF6As an electrolyte solution, the solvent was EC: DEC (volume ratio)v/v ═ 1:1), the cells were assembled and tested for cycling performance at 0.1C rate and rate performance at 0.1C-1C rate.
200mA g-1The specific discharge capacity of the lower first ring is 3200mAh g-1The specific capacity is maintained at 180mAh g after 100 cycles-1(ii) a When the multiplying power is increased to 2000mA g-1Specific discharge capacity of 943mAh g-1. The silicon loading was about 1.4mg/cm-2。
Example 1
Dissolving 0.4g of binder PVDF in 12g of N-methyl pyrrolidone (NMP), stirring for 1h, adding 1.2g of commercial nano silicon powder and 0.4g of super P conductive carbon powder, stirring for 4h, adjusting a scraper to 300 mu m, coating a film on a copper foil in a hanging manner, drying at 65 ℃ overnight, placing 60 mm/60 mm foamed nickel with the thickness of 1mm in one of sulfuric acid aqueous solutions with the pH value of 2.0-5.0 for 10min to carry out activation pretreatment, cleaning the treated foamed nickel with deionized water, and binding the treated foamed nickel with an electrode material through a rubber band to enable the surface of the foamed nickel to be in close contact with the front side and the back side of a self-supporting flexible electrode. Then placing the obtained product in an electroless plating solution at 90 ℃ for 10 minutes to carry out chemical in-situ deposition of metallic nickel, phosphorus and cobalt. The chemical plating solution comprises 20g/L of nickel sulfate; 24g/L sodium hypophosphite; 1ml/L of a 10wt% aqueous PTFE solution; 15g/L sodium citrate; 0.01g/L thiourea; 15g/L sodium acetate; the solution PH was 4.8 and the electroless nickel layer thickness was about 0.5 μm. And drying the electrode with the deposited nickel layer at 65 ℃ overnight, cutting the electrode into small wafers with the diameter of 10mm, weighing the wafers, and performing vacuum drying at 60 ℃ for 24 hours. Subsequent cell assembly was the same as comparative example. The preparation of the electrode slurry is the same as the operation process of the comparative example 1, the electrode slurry is coated on an aluminum film in a blade mode to form a film, the film is quickly immersed into water, the film is taken out after 10min, dried at 65 ℃ overnight, cut into small round pieces with the diameter of 10mm, weighed and dried in vacuum at 60 ℃ for 24 h. Subsequent cell assembly was the same as comparative example. The assembled battery is subjected to a battery cycle performance test at a rate of 0.1C, and a rate performance test at a rate of 0.1C-1C.
200mA g-1The specific discharge capacity of the first circle under the discharge rate is 3246mAh g-1After 100 cycles, the capacity is maintained at 2724mAh g-1(ii) a When the multiplying power is increased to 2000mA g-1Specific capacity of dischargeIs 1600mAh g-1。
Example 2
The operation process of the preparation of the electrode substrate and the chemical plating modification is the same as the operation process of the embodiment 1, the modulation parameter is PTFE aqueous solution with the concentration of 3ml/L and 10wt%, and the assembled battery is subjected to battery cycle performance test at the rate of 0.1C and rate performance test at the rate of 0.1C-1C.
200mA g-1The specific discharge capacity of the first circle under the discharge rate is 3583mAh g-1Capacity after 100 cycles was maintained at 3023mAh g-1(ii) a When the multiplying power is increased to 2000mA g-1Specific discharge capacity of 1954mAh g-1。
As shown in the two figures of FIG. 1, a Ni-P-PTFE coating with metallic luster and dark color is deposited on the surface of the silicon cathode material modified by electroless deposition, and the coating can not only inhibit the problem of capacity attenuation caused by the damage of the peeling of active substances to the whole electrode structure and the like caused by the volume effect (the expansion rate is about 300%) in the process of lithium extraction and lithium insertion of the silicon electrode, but also improve the current collecting effect of the electrode and the electron transmission efficiency in the electrode, and realize higher utilization rate of the active substances
As shown in fig. 2, the batteries assembled in comparative example 1, example 1 and example 2 are used as the batteries of the negative electrode material, and example 1 and example 2 both show higher specific discharge capacity at 0.1C-1C rate than comparative example 1, because compared with comparative example 1, the deposition of the three-dimensional Ni-P-PTFE composite coating of the electrode material is well realized by the electroless deposition technology in examples 1 and 2, so that the current collecting effect is better, the conductive network in the electrode can be strengthened, the utilization rate of the active material is improved, and the deposition coating with elasticity can inhibit the damage of the electrode structure caused by the volume effect in the charging and discharging process of the silicon negative electrode. Thereby further improving the electrochemical performance, and example 2 is the optimal electrode in the rate performance test of the lithium-sulfur battery.
As shown in fig. 3, in the 0.1C battery cycle performance test, examples 1 and 2 also exhibited better cycle performance than comparative example 1, and both the first-cycle specific discharge capacity and the battery capacity after 100 cycles were greater than those of comparative examples 1 and 2. The reason is also that the Ni-P-PTFE coating deposited on the surface of the electrode can improve the current collecting effect and the electron transmission efficiency in the electrode, simultaneously can well inhibit the deformation of the battery and improve the utilization rate of active substances. Example 2 is the optimal electrode in the lithium sulfur battery cycling performance test.
Fig. 4 shows that examples 1 and 2 show smaller electrochemical resistance than comparative example 1 because, as described above, example 1 shows the smallest resistance property because it has the smallest charge transfer resistance because it is deposited with a lower content of PTFE and a higher content of Ni. The cell performance was not as good as that of example 2, which shows that the suppression of the volume effect of the silicon electrode has a larger effect on the cell performance than the electrochemical impedance.
Claims (8)
1. An electrode for a lithium ion battery, characterized in that: the electrode takes foamed nickel as a catalyst, a foamed nickel plate is contacted with the outer surface of a plate-shaped silicon electrode substrate on which a conductive substance is to be deposited, chemical in-situ deposition on the silicon electrode substrate is realized by adopting a contact chemical plating process, so that a nickel-phosphorus composite coating is deposited on the surface and inside of the silicon electrode substrate, and the thickness of the nickel-phosphorus composite coating on the surface of the electrode is 0.3-3 mu m; the silicon electrode substrate comprises an active substance, a conductive carbon material and a binder, or the active substance and the binder; wherein the mass content of the active substance is 60-80%, the mass content of the conductive carbon material is 0-20%, the mass content of the binder is 10-35%, and the mass content of the nickel-phosphorus composite coating on the surface layer and inside the silicon electrode matrix accounts for 1-10wt% of the electrode;
the preparation method comprises the following steps: 1) foam nickel pretreatment: putting the foamed nickel into an aqueous solution of sulfuric acid, hydrochloric acid or nitric acid with the pH value of 2.0-5.0 for 5-20 minutes, and then washing the foamed nickel by deionized water;
2) stacking the pretreated foamed nickel and the electrode surface and the surface opposite layer prepared by the silicon electrode substrate together, fixing the laminated nickel and the electrode surface by using a clamp or a rubber band to ensure that the surfaces of the laminated nickel and the electrode surface are in close contact, and placing the laminated nickel and the electrode surface in chemical plating solution;
3) carrying out chemical plating Ni-P composite coating modification on an electrode material: the chemical plating solution comprises an aqueous solution consisting of nickel salt, a compound solution, a reducing agent, a complexing agent and a buffering agent; the nickel salt is one or more of nickel chloride, nickel sulfate, nickel phosphate and nickel acetate, and the concentration is 10-50 g/L; the composite solution comprises one or more than two of PTFE and PVDF aqueous solutions, and 1-7ml of 10wt% PTFE aqueous solution and/or 10wt% PVDF aqueous solution can be put into each liter of plating solution; the reducing agent is sodium hypophosphite with the mass concentration of 10-50 g/L; the complexing agent is one or more than two of EDTA, EGTA, sodium tartrate and sodium citrate, and the mass concentration is 10-50 g/L; the buffer is one or more than two of sodium acetate, ammonium acetate and ammonium chloride, and the mass concentration is 10-50 g/L;
the pH value of the plating solution is between 4.0 and 5.0 or between 8.0 and 9.5; the temperature is controlled between 60 and 90 during the chemical plating processoAnd C, controlling the time between 15 minutes and 8 hours.
2. The electrode of claim 1, wherein: the conductive carbon material comprises one or more than two of carbon nano tubes, graphene, carbon nano fibers, KB600, KB300 and Super-P.
3. The electrode of claim 1, wherein: the binder is one or more of polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyvinylidene fluoride (PVDF), and polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP).
4. The electrode of claim 1, wherein: the active substance is one or two of silicon oxide, nano silicon particles, porous silicon, silicon/metal and silicon/carbon composite materials.
5. A method of preparing an electrode according to any one of claims 1 to 4, wherein:
1) foam nickel pretreatment: putting the foamed nickel into an aqueous solution of sulfuric acid, hydrochloric acid or nitric acid with the pH value of 2.0-5.0 for 5-20 minutes, and then washing the foamed nickel by deionized water;
2) stacking the pretreated foamed nickel and the electrode surface and the surface opposite layer prepared by the silicon electrode substrate of claims 1-4 together, fixing the laminated nickel by using a clamp or a rubber band to ensure that the surface of the laminated nickel is in close contact with the surface of the laminated nickel, and placing the laminated nickel in chemical plating solution;
3) carrying out chemical plating Ni-P composite coating modification on an electrode material: the chemical plating solution comprises an aqueous solution consisting of nickel salt, a compound solution, a reducing agent, a complexing agent and a buffering agent; the nickel salt is one or more of nickel chloride, nickel sulfate, nickel phosphate and nickel acetate, and the concentration is 10-50 g/L; the composite solution comprises one or more than two of PTFE and PVDF aqueous solutions, and 1-7ml of 10wt% PTFE aqueous solution and/or 10wt% PVDF aqueous solution can be put into each liter of plating solution; the reducing agent is sodium hypophosphite with the mass concentration of 10-50 g/L; the complexing agent is one or more than two of EDTA, EGTA, sodium tartrate and sodium citrate, and the mass concentration is 10-50 g/L; the buffer is one or more than two of sodium acetate, ammonium acetate and ammonium chloride, and the mass concentration is 10-50 g/L;
the pH value of the plating solution is between 4.0 and 5.0 or between 8.0 and 9.5; the temperature is controlled between 60 and 90 during the chemical plating processoAnd C, controlling the time between 15 minutes and 8 hours.
6. The method according to claim 5, wherein the electroless plating solution further comprises a stabilizer selected from the group consisting of sodium thiosulfate, potassium iodide and thiourea, and the mass concentration of the stabilizer is 0.01 to 0.1 g/L.
7. The method according to claim 5, wherein the pH of the plating solution is adjusted by using a pH adjusting agent selected from the group consisting of a hydrochloric acid or sulfuric acid solution having a concentration of 100-400g/L and a sodium hydroxide or ammonia aqueous solution having a concentration of 40-160 g/L.
8. Use of the electrode according to claim 1 as a negative electrode in a secondary lithium ion battery consisting of a positive electrode, a membrane and a negative electrode.
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| CN105274504A (en) * | 2015-11-27 | 2016-01-27 | 中国科学院电工研究所 | Method for chemically plating copper on surface of expanded graphite |
| CN106486647A (en) * | 2015-08-31 | 2017-03-08 | 华为技术有限公司 | A kind of composite cathode material for lithium ion cell and preparation method thereof and lithium ion battery |
| CN107394138A (en) * | 2017-07-04 | 2017-11-24 | 中国科学院上海高等研究院 | Lithium ion battery negative material structure, lithium ion battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106486647A (en) * | 2015-08-31 | 2017-03-08 | 华为技术有限公司 | A kind of composite cathode material for lithium ion cell and preparation method thereof and lithium ion battery |
| CN105274504A (en) * | 2015-11-27 | 2016-01-27 | 中国科学院电工研究所 | Method for chemically plating copper on surface of expanded graphite |
| CN107394138A (en) * | 2017-07-04 | 2017-11-24 | 中国科学院上海高等研究院 | Lithium ion battery negative material structure, lithium ion battery and preparation method thereof |
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