Background
In order to realize sustainable development of society and environment, renewable energy and clean energy are being explored and researched in various countries of the world. Solar energy, wind energy and the like are alternative green clean energy sources, but the clean energy sources cannot be directly utilized and energy storage and conversion devices are needed, so that various batteries are developed vigorously. Among them, lithium ion batteries are gradually replacing nickel-metal hydride batteries, lead-acid batteries, nickel-cadmium batteries and the like due to their advantages of large energy density, long cycle life, high working voltage, small self-discharge rate, environmental friendliness, large specific power and the like, and provide possibility for storage and wide use of clean energy.
Among the electrode materials of lithium ion batteries which are commercialized at present, graphite materials are most widely used and the technology is the most mature. Graphite materials have not been able to meet the demands of next generation batteries due to their own drawbacks. Firstly, the theoretical specific capacity of the graphite material is too low, and is only 372mAh g-1; meanwhile, the safety problem is easily caused because the working voltage is too low. The silicon material has extremely high theoretical specific capacity (4200mAh g-1), lower electrochemical reaction voltage (less than 0.5V), environmental friendliness and abundant resource reserves, arouses the attention of more and more researchers, and is considered to be one of the most promising materials capable of replacing graphite to become the next generation of lithium ion battery cathode materials.
Although silicon has many advantages as a negative electrode material for lithium ion batteries, it also has some problems. Because of the diamond structure of silicon, lithium ions can form lithium-silicon alloy with silicon when being embedded, and the original structure is broken, so that the volume expansion of over 300% can occur to the silicon electrode after lithium is embedded in the circulation, and the volume of the silicon cathode is shrunk back when lithium is removed, so that the large volume change can lead to the pulverization of the silicon cathode material in the continuous circulation, and the silicon cathode material is separated from the surface of the collector to lose chemical activity, thereby causing the capacity loss of the lithium battery. In addition, electrolyte on the surface of the silicon negative electrode can be degraded to generate a solid electrolyte layer (SEI film) to wrap the electrode during lithium intercalation, and the solid electrolyte layer can be cracked and regenerated continuously along with the volume change of the electrode, so that the electrolyte is consumed continuously, and the low cycle efficiency and the short cycle life are caused.
Therefore, in order to improve the cycle life of the silicon negative electrode and prevent the silicon electrode from being crushed due to expansion and contraction of the silicon electrode, it is necessary to develop a grid-type stacked structure nano conductive fiber silicon negative electrode and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a silicon cathode integrated by synthesizing and molding a grid type laminated structure material, which solves the problem of poor battery cycle performance caused by damage to the overall structure of the silicon cathode due to volume expansion of silicon particles in the cathode charge-discharge process in the prior art.
The invention also aims to provide a preparation method of the silicon anode which is synthesized and molded integrally by the grid type laminated structural material.
The technical scheme adopted by the invention is that a grid type laminated structure material is synthesized and formed into an integrated silicon cathode, which consists of silicon particles, an organic metal salt conductive precursor and a spinning polymer; based on the spinning polymer, the mass ratio of the organic metal salt to the spinning polymer is 1: 100-10, wherein the mass ratio of the silicon powder to the spinning polymer is 1: 10-1.
The invention adopts another technical scheme that the preparation method of the integrated silicon cathode formed by synthesizing the grid type laminated structure material is implemented according to the following steps:
step 1: preparing an organic metal salt conductive precursor,
dissolving a metal salt in a mixed solvent A of deionized water and absolute ethyl alcohol to obtain a mixed solution A; putting the mixed solution A into ice water for water bath stirring, adding a ligand, and quickly stirring after the addition is finished; then, adding a reducing agent into the stirred solution, and stirring to obtain an organic metal salt conductive precursor;
step 2: preparing a spinning solution, namely preparing a spinning solution,
adding the organic metal salt conductive precursor into a mixed solvent B of anhydrous ethanol and deionized water to obtain a mixed solution B; stirring at room temperature, adding a spinning polymer, and stirring at room temperature to obtain a spinning solution of the conductive nanofiber;
and step 3: the addition of the silicon particles is carried out,
adding silicon particles into the spinning solution, and stirring until the silicon particles are uniformly dispersed to obtain a mixed solution C;
and 4, step 4: carrying out electrostatic spinning to the mixture to obtain the fiber,
injecting the mixed solution C into an injector, discharging air bubbles, installing a spinning needle, spinning, and collecting the composite nanofiber membrane by using copper foil;
and 5: the slices are calcined and then cut into pieces,
and calcining the composite nanofiber membrane, and slicing to obtain the composite nanofiber membrane.
The beneficial effects of the invention comprise the following aspects:
1) the silicon cathode material with the grid-type laminated fiber structure is prepared from the organic metal salt conductive precursor, the spinning solution and the silicon particles, and the capacity of the battery can be improved. The fiber material is attached to the polar plate after being calcined, so that the falling of the electrode material is prevented.
2) The silicon negative electrode material prepared has a grid type laminated fiber structure, silicon particles are attached to the nano conductive fibers, and the fibers have certain flexibility, so that the negative electrode structure can be maintained to be unlikely to be damaged during charging and discharging, and meanwhile, gaps among the fibers can provide enough space for volume expansion in the charging and discharging processes of the silicon particle silicon negative electrode, so that the expansion of the silicon negative electrode is accommodated, the integral structure of the silicon negative electrode is prevented from being damaged, and the cycle performance of the battery is improved.
3) Meanwhile, the grid type laminated structure has a large specific surface area, a soaking field can be provided for electrolyte in the silicon cathode, and the cycle performance of the battery is improved.
4) The silicon particles are directly contacted with the conductive fibers, and the conductive fibers are contacted with the copper foil, so that the silicon particles are connected with the copper foil through the nano-fiber conductive network, the contact rate of the silicon particles is improved, the battery capacity is improved, and the cycle performance is improved.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to an integrated silicon cathode synthesized by a grid-type laminated structure material, which consists of silicon particles, an organic metal salt conductive precursor and a spinning polymer. Based on the spinning polymer, the mass ratio of the organic metal salt to the spinning polymer is 1: 100-10, wherein the mass ratio of the silicon powder to the spinning polymer is 1: 10-1.
The metal salt is selected from silver nitrate, silver acetate and copper nitrate;
the ammonia ligand used by the conductive precursor is ethanolamine, isopropylamine or ammonia water;
the silicon particles have a particle size of 50-500 nm.
The invention discloses a preparation method of a grid type laminated structure material synthesis and molding integrated silicon cathode, which is implemented according to the following steps:
step 1: preparing an organic metal salt conductive precursor,
dissolving a metal salt in a mixed solvent A of deionized water and absolute ethyl alcohol (the ratio of the metal salt to the mixed solvent A is 1g/100mL to 10g/100mL, the ratio of the deionized water to the absolute ethyl alcohol is 1-5: 5-1, and the dosage requirement is loose and can not be too thin or too thick) to obtain a mixed solution A; placing the mixed solution A into ice water, stirring in water bath, adding ligand (ethanolamine, isopropylamine or ammonia water, 0.5-5 g of metal salt per ml of ligand), and rapidly stirring for 5-50 min; then, adding a reducing agent (N, N-dimethylformamide or ethylene glycol, 0.1g-10g of metal salt is prepared in each milliliter of the reducing agent) into the stirred solution, and stirring for 15-50min to obtain an organic metal salt conductive precursor;
step 2: preparing a spinning solution, namely preparing a spinning solution,
adding the organic metal salt conductive precursor into a mixed solvent B of absolute ethyl alcohol and deionized water (the volume ratio of the organic metal salt conductive precursor to the mixed solvent B is 1: 2-10, and the ratio of the deionized water to the absolute ethyl alcohol is 1-5: 5-1.) to obtain a mixed solution B; stirring for 15-50min at room temperature, adding spinning polymer (polyvinylpyrrolidone (PVP) or PEO) which is 5-40% of the total mass of the mixed solution B, and stirring for 5-20h at room temperature to obtain spinning solution of conductive nanofiber;
and step 3: the addition of the silicon particles is carried out,
adding silicon particles into the spinning solution, wherein the ratio of the silicon particles to the spinning solution is 1-20g/100mL, and mixing and stirring the silicon particles and the spinning solution until the silicon particles and the spinning solution are uniformly dispersed to obtain a mixed solution C;
and 4, step 4: carrying out electrostatic spinning to the mixture to obtain the fiber,
injecting the mixed solution C into an injector, discharging air bubbles, installing a spinning needle, setting spinning parameters on an electrostatic spinning machine, adjusting the distance between polar plates, voltage and flow rate, spinning, and collecting the composite nanofiber membrane by using copper foil;
and 5: the slices are calcined and then cut into pieces,
calcining the composite nanofiber membrane at the temperature of 150-500 ℃ for 30-150min, and slicing to obtain the composite nanofiber membrane.
Referring to fig. 1, the silicon anode is a silicon anode integrated by synthesizing a grid-type laminated structure material prepared by the method of the present invention, and the nano-silicon particles 1 are attached to the nano-conductive fiber grid 2, so the product prepared by the present invention is called a silicon anode integrated by synthesizing a grid-type laminated structure material.
Example 1
Step 1: preparing an organic metal salt conductive precursor,
dissolving 0.45g of silver nitrate powder in 20mL of a mixed solvent A of deionized water and absolute ethyl alcohol (the ratio of the deionized water to the absolute ethyl alcohol is 1: 1) to obtain a mixed solution A; placing the mixed solution A into ice water for water bath stirring, adding 0.6mL of isopropylamine, and quickly stirring for 15min after the addition is finished; then, adding 1mL of reducing agent ethylene glycol into the stirred solution, and stirring for 30min to obtain an organic metal salt conductive precursor;
step 2: preparing a spinning solution, namely preparing a spinning solution,
adding 20mL of organic metal salt conductive precursor into 50mL of mixed solvent B of absolute ethyl alcohol and deionized water (the ratio of the deionized water to the absolute ethyl alcohol is 1: 1) to obtain mixed solution B; stirring for 30min at room temperature, adding 18% by mass of polyvinylpyrrolidone (PVP), and stirring for 12h at room temperature to obtain a spinning solution of the conductive nanofiber;
and step 3: the addition of the silicon particles is carried out,
adding silicon particles with the particle size of 100nm into the spinning solution, wherein the ratio of the silicon particles to the spinning solution is 5g/100mL, and mixing and stirring the silicon particles and the spinning solution until the silicon particles and the spinning solution are uniformly dispersed to obtain a mixed solution C;
and 4, step 4: carrying out electrostatic spinning to the mixture to obtain the fiber,
injecting the mixed solution C into an injector, discharging air bubbles, installing a spinning needle, setting spinning parameters on an electrostatic spinning machine, adjusting the distance between polar plates to be 14cm, adjusting the voltage to be 16kV and adjusting the flow rate to be 3.0mL/h, spinning, and collecting the composite nanofiber membrane by using copper foil;
and 5: the slices are calcined and then cut into pieces,
and calcining the composite nanofiber membrane at 270 ℃ for 60min, and slicing to obtain the composite nanofiber membrane.
Example 2
Step 1: preparing an organic metal salt conductive precursor,
dissolving 1.4g of silver nitrate powder in 20mL of a mixed solvent A of deionized water and absolute ethyl alcohol (the ratio of the deionized water to the absolute ethyl alcohol is 2: 1) to obtain a mixed solution A; placing the mixed solution A into ice water for water bath stirring, adding 0.6mL of isopropylamine, and quickly stirring for 15min after the addition is finished; then, adding 2mL of reducing agent ethylene glycol into the stirred solution, and stirring for 30min to obtain an organic metal salt conductive precursor;
step 2: preparing a spinning solution, namely preparing a spinning solution,
adding 20mL of organic metal salt conductive precursor into 50mL of mixed solvent B of absolute ethyl alcohol and deionized water (the ratio of the deionized water to the absolute ethyl alcohol is also 2: 1) to obtain mixed solution B; stirring for 30min at room temperature, adding 20% polyvinylpyrrolidone (PVP) by mass, and stirring for 12h at room temperature to obtain a spinning solution of the conductive nanofiber;
and step 3: the addition of the silicon particles is carried out,
adding silicon particles with the particle size of 250nm into the spinning solution, wherein the ratio of the silicon particles to the spinning solution is 8g/100mL, and mixing and stirring the silicon particles and the spinning solution until the silicon particles and the spinning solution are uniformly dispersed to obtain a mixed solution C;
and 4, step 4: carrying out electrostatic spinning to the mixture to obtain the fiber,
injecting the mixed solution C into an injector, discharging air bubbles, installing a spinning needle, setting spinning parameters on an electrostatic spinning machine, adjusting the distance between polar plates to be 14cm, adjusting the voltage to be 16kV and adjusting the flow rate to be 3.0mL/h, spinning, and collecting the composite nanofiber membrane by using copper foil;
and 5: the slices are calcined and then cut into pieces,
calcining the composite nanofiber membrane at 300 ℃ for 80min, and slicing to obtain the composite nanofiber membrane.
Example 3
Step 1: preparing an organic metal salt conductive precursor,
dissolving 0.5g of silver nitrate powder in 20mL of a mixed solvent A of deionized water and absolute ethyl alcohol (the ratio of the deionized water to the absolute ethyl alcohol is 1: 2) to obtain a mixed solution A; placing the mixed solution A into ice water for water bath stirring, adding 0.5mL of isopropylamine, and quickly stirring for 25min after the addition is finished; then, adding 3mL of reducing agent ethylene glycol into the stirred solution, and stirring for 50min to obtain an organic metal salt conductive precursor;
step 2: preparing a spinning solution, namely preparing a spinning solution,
adding 30mL of organic metal salt conductive precursor into 60mL of mixed solvent B of absolute ethyl alcohol and deionized water (the ratio of the deionized water to the absolute ethyl alcohol is also 2: 1) to obtain mixed solution B; stirring for 30min at room temperature, then adding PEO with the mass fraction of 23%, and stirring for 10h at room temperature to obtain a spinning solution of the conductive nanofiber;
and step 3: the addition of the silicon particles is carried out,
adding silicon particles with the particle size of 100nm into the spinning solution, wherein the ratio of the silicon particles to the spinning solution is 10g/100mL, and mixing and stirring the silicon particles and the spinning solution until the silicon particles and the spinning solution are uniformly dispersed to obtain a mixed solution C;
and 4, step 4: carrying out electrostatic spinning to the mixture to obtain the fiber,
injecting the mixed solution C into an injector, discharging air bubbles, installing a spinning needle, setting spinning parameters on an electrostatic spinning machine, adjusting the distance between polar plates to be 14cm, adjusting the voltage to be 16kV and adjusting the flow rate to be 3.0mL/h, spinning, and collecting the composite nanofiber membrane by using copper foil;
and 5: the slices are calcined and then cut into pieces,
and (3) calcining the composite nanofiber membrane at 250 ℃ for 100min, and slicing to obtain the composite nanofiber membrane.
Example 4
Step 1: preparing an organic metal salt conductive precursor,
dissolving 1.4g of silver nitrate powder in 20mL of a mixed solvent A of deionized water and absolute ethyl alcohol (the ratio of the deionized water to the absolute ethyl alcohol is 3: 1) to obtain a mixed solution A; placing the mixed solution A into ice water for water bath stirring, adding 0.9mL of isopropylamine, and quickly stirring for 30min after the addition is finished; then, adding 3mL of reducing agent ethylene glycol into the stirred solution, and stirring for 45min to obtain an organic metal salt conductive precursor;
step 2: preparing a spinning solution, namely preparing a spinning solution,
adding 20mL of organic metal salt conductive precursor into 50mL of mixed solvent B of absolute ethyl alcohol and deionized water (the ratio of the deionized water to the absolute ethyl alcohol is 3: 1) to obtain mixed solution B; stirring for 30min at room temperature, adding 40% polyethylene oxide (PEO) by mass, and stirring for 9h at room temperature to obtain a spinning solution of the conductive nanofiber;
and step 3: the addition of the silicon particles is carried out,
adding silicon particles with the particle size of 200nm into the spinning solution, wherein the ratio of the silicon particles to the spinning solution is 6g/100mL, and mixing and stirring the mixture until the mixture is uniformly dispersed to obtain a mixed solution C;
and 4, step 4: carrying out electrostatic spinning to the mixture to obtain the fiber,
injecting the mixed solution C into an injector, discharging air bubbles, installing a spinning needle, setting spinning parameters on an electrostatic spinning machine, adjusting the distance between polar plates to be 14cm, adjusting the voltage to be 16kV and adjusting the flow rate to be 3.0mL/h, spinning, and collecting the composite nanofiber membrane by using copper foil;
and 5: the slices are calcined and then cut into pieces,
and calcining the composite nanofiber membrane at 300 ℃ for 120min, and slicing to obtain the composite nanofiber membrane.
Example 5
Step 1: preparing an organic metal salt conductive precursor,
dissolving 0.45g of copper nitrate powder in 20mL of a mixed solvent A of deionized water and absolute ethyl alcohol (the ratio of the deionized water to the absolute ethyl alcohol is 1: 2) to obtain a mixed solution A; putting the mixed solution A into ice water for water bath stirring, adding 0.6mL of ammonia water, and quickly stirring for 15min after the addition is finished; then, adding 3mL of reducing agent ethylene glycol into the stirred solution, and stirring for 30min to obtain an organic metal salt conductive precursor;
step 2: preparing a spinning solution, namely preparing a spinning solution,
adding 15mL of organic metal salt conductive precursor into 60mL of mixed solvent B of absolute ethyl alcohol and deionized water (the ratio of the deionized water to the absolute ethyl alcohol is 1: 2) to obtain mixed solution B; stirring for 30min at room temperature, adding polyvinylpyrrolidone (PVP) with the mass fraction of 40%, and stirring for 12h at room temperature to obtain a spinning solution of the conductive nanofiber;
and step 3: the addition of the silicon particles is carried out,
adding silicon particles with the particle size of 300nm into the spinning solution, wherein the ratio of the silicon particles to the spinning solution is 3g/100mL, and mixing and stirring the mixture until the mixture is uniformly dispersed to obtain a mixed solution C;
and 4, step 4: carrying out electrostatic spinning to the mixture to obtain the fiber,
injecting the mixed solution C into an injector, discharging air bubbles, installing a spinning needle, setting spinning parameters on an electrostatic spinning machine, adjusting the distance between polar plates to be 14cm, adjusting the voltage to be 16kV and adjusting the flow rate to be 3.0mL/h, spinning, and collecting the composite nanofiber membrane by using copper foil;
and 5: the slices are calcined and then cut into pieces,
calcining the composite nanofiber membrane at 450 ℃ for 30min, and slicing to obtain the composite nanofiber membrane.
Example 6
Step 1: preparing an organic metal salt conductive precursor,
dissolving 0.4g of silver acetate powder in 20mL of a mixed solvent A of deionized water and absolute ethyl alcohol (the ratio of the deionized water to the absolute ethyl alcohol is 5: 1) to obtain a mixed solution A; placing the mixed solution A into ice water for water bath stirring, adding 0.6mL of ethanolamine, and rapidly stirring for 25min after the addition is finished; then, adding 1mL of reducing agent N, N-dimethylformamide into the stirred solution, and stirring for 30min to obtain an organic metal salt conductive precursor;
step 2: preparing a spinning solution, namely preparing a spinning solution,
adding 15mL of organic metal salt conductive precursor into 60mL of mixed solvent B of absolute ethyl alcohol and deionized water (the ratio of the deionized water to the absolute ethyl alcohol is 5: 1) to obtain mixed solution B; stirring for 30min at room temperature, adding polyvinylpyrrolidone (PVP) with the mass fraction of 36%, and stirring for 12h at room temperature to obtain a spinning solution of the conductive nanofiber;
and step 3: the addition of the silicon particles is carried out,
adding silicon particles with the particle size of 400nm into the spinning solution, wherein the ratio of the silicon particles to the spinning solution is 15g/100mL, and mixing and stirring the silicon particles and the spinning solution until the silicon particles and the spinning solution are uniformly dispersed to obtain a mixed solution C;
and 4, step 4: carrying out electrostatic spinning to the mixture to obtain the fiber,
injecting the mixed solution C into an injector, discharging air bubbles, installing a spinning needle, setting spinning parameters on an electrostatic spinning machine, adjusting the distance between polar plates to be 14cm, adjusting the voltage to be 16kV and adjusting the flow rate to be 3.0mL/h, spinning, and collecting the composite nanofiber membrane by using copper foil;
and 5: the slices are calcined and then cut into pieces,
calcining the composite nanofiber membrane at 150 ℃ for 150min, and slicing to obtain the composite nanofiber membrane.
Performance testing
Testing the specific capacity of the battery: the specific capacity test is to cut the coated single-sided pole piece into a wafer with the diameter of 15mm, then use the lithium sheet as a counter electrode to manufacture a CR2016 button battery, and test the button battery on test equipment to obtain the material performance. The test results are shown in table 1.
And (3) testing the cycle performance: the button half-cell is circularly scanned by controlling a certain voltage range, the current magnitude at different voltages is recorded, and the electrochemical reaction mechanism of the electrode material is determined by the voltage interval of each current peak. The test cell was charged with 80mA constant current for 960min, limited to 4.2V, and 160mA constant current to 3.0V, and then its initial capacity was obtained. The discharging step was repeated 50 times, and the discharge capacity after 50 cycles was recorded, and the discharge capacity retention rate was calculated according to the following formula. The test results are shown in table 1.
The retention ratio of discharge capacity was defined as discharge capacity after 50 cycles/initial discharge capacity × 100%
TABLE 1 Performance test results for six examples of the invention
As can be seen from the above table, the silicon cathode synthesized and formed integrally from the grid-type laminated structure material prepared by the invention has higher specific capacity and better rate discharge characteristic compared with the existing silicon cathode, the performance of the existing silicon cathode is further improved, and the requirement of the existing high-performance battery is further met.