CN113972362B - Active composite material for lithium ion battery and preparation method thereof - Google Patents
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Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to an active composite material for a lithium ion battery and a preparation method thereof. The active composite material consists of silicon micro-nano particles, graphite and graphene, and comprises the following components in percentage by mass: 20-40% of silicon micro-nano particles, 3-8% of graphene and the balance of graphite. According to the invention, silicon micro-nano particles and weak graphite oxide are used as precursors, and the high-performance silicon/graphite/graphene composite material is obtained through one-step high-temperature ball milling treatment, so that the preparation method is simple and is beneficial to large-scale mass production.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an active composite material for a lithium ion battery and a preparation method thereof.
Background
Among various secondary batteries, lithium ion batteries have the advantages of high energy density, long cycle life, no memory effect and the like, and are main power supply devices of new energy automobiles. The development of lithium ion batteries with higher energy density is a key research and development direction of current major manufacturers to solve the mileage anxiety of new energy automobile users. In order to achieve the above object, the use of novel electrode materials with high specific energy is the main technical route. In various novel electrode materials, the theoretical specific capacity of silicon is up to 4200mAh/g, which is much higher than that of the traditional graphite negative electrode (372 m)Ah/g) and rich earth crust reserves and wide sources, and is an ideal electrode material for the next generation of lithium ion batteries. However, the conductivity of silicon is low (2.54 × 10) -4 S/m), and the volume change is large (300%) in the process of lithium ion intercalation/deintercalation, which is likely to cause the growth of SEI film and the damage of electrode structure, and the cycle performance is poor, limiting its practical application effect.
Among various materials, the carbon material has high conductivity and chemical stability, and is an ideal composite material of a silicon-based negative electrode. Common composite carbon materials include graphite, graphene, carbon nanotubes, amorphous carbon, and the like. The graphite is low in price and stable in mechanical structure, can be used as a silicon supporting framework, effectively inhibits the volume change of silicon, and is the first choice for commercialization. At present, the silicon/graphite composite material is mainly prepared by a physical mixing (mechanical ball milling/spray drying) mode, and key problems which are not solved are as follows: 1. the silicon and the graphite are mixed loosely, the interface bonding force is weak, and the synergistic lithium storage effect of the silicon and the graphite is difficult to exert; 2. when the graphite is difficult to resist the large stress released in the charge and discharge process of silicon under high loading, the structural damage is generated; 3. graphite has a low specific surface area and a weak loading capacity for silicon, and the loading capacity of silicon is also limited. Although the problems can be alleviated by coating modification of the surface of the silicon particles and addition of the nanocarbon material, the existing process increases the complexity and cost of the preparation process and introduces the problem of homogeneous mixing of different materials.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides an active composite material for a lithium ion battery, which can increase the specific capacity and the cycling stability of an electrode.
The purpose of the invention can be realized by the following technical scheme:
an active composite material for a lithium ion battery is composed of silicon micro-nano particles, graphite and graphene, and comprises the following components in percentage by mass: 20-40% of silicon micro-nano particles, 3-8% of graphene and the balance of graphite.
Preferably, the composite material comprises the following components in percentage by mass: 20-35% of silicon micro-nano particles, 3-5% of graphene and the balance of graphite.
In the active composite material for the lithium ion battery, the particle size of the silicon micro-nano particles is 60-200nm. The particle size of the silicon micro-nano particles needs to be controlled, and the silicon nano particles with the undersize particle size have poor dispersibility and are easy to agglomerate; on the other hand, silicon nanoparticles having an excessively large particle size are difficult to be inserted between the graphite exfoliation layers, and the contact strength between the two is reduced.
The invention also provides a preparation method of the active composite material for the lithium ion battery, which comprises the following steps:
s1, carrying out weak oxidation treatment on graphite;
s2, mixing the graphite subjected to weak oxidation treatment with the silicon micro-nano particles, and performing high-speed ball milling in an argon atmosphere;
and S3, carrying out medium-speed high-temperature ball milling in an argon atmosphere to obtain the silicon/graphite/graphene active composite material.
According to the invention, on the basis of a conventional process, graphite is subjected to weak oxidation treatment, and then silicon micro-nano particles and weak graphite oxide are adopted as precursors, and a high-performance silicon/graphite/graphene active composite material is obtained through one-step high-temperature ball milling treatment, so that the interface bonding force between silicon and graphite is enhanced, and the cooperative protection of 'hardness and softness' of silicon is realized.
In the above method for preparing an active composite material for a lithium ion battery, the step S1 of weak oxidation treatment specifically includes: adding graphite into ice bath concentrated sulfuric acid, adding potassium permanganate, uniformly mixing, adding hydrogen peroxide and deionized water, reacting, washing with hydrochloric acid and deionized water, and drying in vacuum to obtain weakly oxidized graphite.
The weak graphite oxide can perform a reduction reaction in a high-temperature ball milling process, and under the action of mechanical friction, the weak graphite oxide can perform lamellar stripping to form small-size particles and a small amount of graphene; in the process, the silicon micro-nano particles can be embedded into the interlayer structure of the graphite, and the bonding force of the silicon micro-nano particles and the interlayer structure of the graphite is increased, so that the uniformly dispersed silicon/graphite/graphene composite material is obtained.
Preferably, the addition amount of concentrated sulfuric acid is 100-120ml per 1g of graphite.
Preferably, the potassium permanganate is added, then the mixture is stirred for 10-20min, then the temperature is raised to 50-55 ℃, the reaction is carried out for 3-4h at the temperature, and then the mixture is cooled to the room temperature.
Preferably, the concentration of the hydrogen peroxide is 25-35%, and the reaction time is 5-8h after the hydrogen peroxide and the deionized water are added.
In the preparation method of the active composite material for the lithium ion battery, the mass ratio of the graphite to the potassium permanganate is 1 (1.5-4.0).
In the preparation method of the active composite material for the lithium ion battery, the vacuum drying temperature is 95-120 ℃ and the time is 8-15h.
In the preparation method of the active composite material for the lithium ion battery, the mass ratio of the graphite subjected to weak oxidation treatment to the silicon micro-nano particles in the step S2 is (2.5-4): 1. When the too high silicon loading easily causes the agglomeration of silicon particles and the reduction of the composite effect, the graphite/graphene composite structure is difficult to completely support all silicon nanoparticles, thereby causing the reduction of the protection effect on the silicon nanoparticles.
In the preparation method of the active composite material for the lithium ion battery, in the high-speed ball milling in the step S2, the rotating speed of a ball milling tank is set to be 250-350rpm in self-transmission and 700-1000rpm in revolution, and the high-speed ball milling time is 2-3h.
In the preparation method of the active composite material for the lithium ion battery, in the step S3, the rotation speed of a ball milling tank in the medium-speed and high-temperature ball milling is set to be 150-250rpm in self-transmission and 300-500rpm in revolution; the time of the medium-speed ball milling is 15-18h.
In the above preparation method of the active composite material for the lithium ion battery, the temperature of the medium-speed high-temperature ball milling in the step S3 is 300-500 ℃.
Under the argon atmosphere, reduce the rotational speed of ball mill, improve the cavity temperature of ball mill, further ball-milling dispersion treatment, can make graphite oxide reduction and reduce the particle size of graphite, make the fine grain embedding graphite layer of receiving a little of silicon simultaneously, obtain silicon/graphite alkene combined material, it is too fast to need to notice if the ball-milling speed is too fast in high temperature intermediate speed ball-milling, the shearing action that graphite received is strengthened, lead to violent lamella peeling phenomenon easily, form too much graphite alkene, increase combined material's specific surface area, thereby can lead to the reduction of first coulomb efficiency.
The invention also provides a negative pole piece which comprises the active composite material. The preparation method comprises the following steps: and mixing the active composite material, carbon black and a binder PVDF in NMP to prepare uniformly dispersed negative electrode slurry, coating the slurry on a copper foil, and drying in vacuum to obtain the negative electrode plate.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, silicon micro-nano particles and weak graphite oxide are used as precursors, and a high-performance silicon/graphite/graphene composite material is obtained through one-step high-temperature ball milling treatment, so that the preparation method is simple and is beneficial to large-scale mass production;
2. in the active composite material, the silicon and the graphite are tightly combined, and the synergistic lithium storage effect of the graphite and the silicon can be improved, so that the effective utilization rate of silicon particles is improved, and the specific capacity of an electrode is increased;
3. in the active composite material, the small-sized rigid graphite particles can inhibit the volume expansion of silicon, avoid the structural damage caused by the volume expansion of the particles and increase the cycle stability;
4. in the active composite material, the flexible graphene sheet can improve the load capacity of silicon particles, and simultaneously ensure the electrical contact with a conductive network in the circulation process, thereby increasing the circulation stability.
Drawings
Fig. 1 is a scanning electron micrograph of the silicon/graphite/graphene active composite material obtained in example 1.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example 1:
s1, firstly, adding 1.0g of natural crystalline flake graphite into 100ml of ice-bath concentrated sulfuric acid, and then slowly adding 3.5g of potassium permanganate;
s2, stirring for 15min, heating to 50 ℃, reacting for 4h at the temperature, and then cooling to room temperature;
s3, pouring 8mL of 30% hydrogen peroxide and 100mL of deionized water, and reacting for 6h;
s4, washing with 5% hydrochloric acid and deionized water in sequence, and drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain weak graphite oxide;
s5, mixing weak graphite oxide with silicon micro-nano particles with the particle size of 100nm according to the mass ratio of 2.5; subsequently, high-speed ball milling was performed under an argon atmosphere: the autorotation speed of the ball milling tank is 300rpm, the revolution speed is 900rpm, and the ball milling time is 3 hours;
s6, heating the ball milling tank to 300 ℃ in an argon atmosphere, and carrying out medium-speed ball milling for 16h at the rotation speed of 150rpm and the revolution speed of 500rpm to obtain the silicon/graphite/graphene active composite material;
s7, mixing the active composite material, carbon black and a binder PVDF in NMP according to a mass ratio of 8 2 )；
S8, assembling the negative pole piece and the lithium piece into a button cell, and adopting 1MLiPF 6 FEC/EMC as electrolyte, performance testing.
Example 2:
the difference from the example 1 is only that in the step S5, the weak graphite oxide is taken according to the mass ratio of 3.5.
Example 3:
the difference from the example 1 is only that in the step S5, the weak graphite oxide is taken according to the mass ratio of 4.0.
Example 4:
the only difference from example 1 is that the ball milling time in step S6 was 10 hours.
Example 5:
the difference from example 1 is only that the silicon micro-nano particles have a particle size of 30nm.
Example 6:
the difference from example 1 is only that the silicon micro-nano particles have a particle size of 250nm.
Example 7:
the only difference from example 1 is that step S6 was performed without performing the temperature-raising treatment of the ball mill pot under an argon atmosphere.
Example 8:
the only difference from example 1 is that the medium speed ball milling treatment in step S6 was not performed.
Example 9:
the only difference from example 1 is that the graphite was not subjected to the weak oxidation treatment.
Comparative example 1:
the only difference from example 1 is that the composite material does not contain silicon micro-nano particles.
And (3) performance detection: and (3) carrying out constant current charging and discharging on the button cell for 5 circles by adopting a multiplying power of 0.2C, and then circulating for 500 times by adopting a multiplying power of 1C.
Table 1: examples 1-4 active composite Material Performance test results
Fig. 1 is a scanning electron micrograph of the silicon/graphite/graphene active composite material obtained in example 1. It can be seen that the natural crystalline flake graphite is cut into small-sized graphite flakes after ball milling, the silicon micro-nano particles are embedded into the stripping layers of the graphite, and meanwhile, part of thin graphene is generated, and the graphite and the silicon micro-nano particles are dispersed on the graphene substrate.
From examples 1 to 3, it can be seen that the specific capacity of the silicon/graphite/graphene active composite material of the present invention can reach the market-leading level. With the reduction of the silicon content, the cycle performance of the composite material can be further improved, and when the silicon loading is 20wt%, the capacity retention rate of 500 cycles can reach more than 80%.
From examples 5-6, it can be seen that both too small and too large silicon nanoparticles reduce the composite effect of the composite, resulting in a rapid capacity fade.
As can be seen from example 7, without high temperature treatment, the graphite oxide is difficult to be sufficiently reduced, and a hybridization reaction of introducing a functional group leads to rapid capacity fade.
As can be seen from examples 4 and 8, the absence of high temperature ball milling or the reduction of the medium speed ball milling time reduces the cycle stability, possibly the size of the graphite particles is not effectively reduced and the silicon nanoparticles are not intercalated between the exfoliated layers of graphite.
It can be seen from example 9 that, without weak oxidation treatment of graphite, graphite is difficult to be exfoliated during ball milling, a graphene/graphite composite structure cannot be formed, and meanwhile, silicon nanoparticles are difficult to be intercalated between layers, and the cycle stability is greatly reduced.
The technical range of the embodiment of the invention is not exhaustive, and new technical solutions formed by equivalent replacement of single or multiple technical features in the technical solutions of the embodiment are also within the scope of the invention; in all the embodiments of the present invention, which are listed or not listed, each parameter in the same embodiment only represents an example (i.e., a feasible embodiment) of the technical solution, and there is no strict matching and limiting relationship between the parameters, wherein the parameters may be replaced with each other without departing from the axiom and the requirements of the present invention, unless otherwise specified.
The technical means disclosed by the scheme of the invention are not limited to the technical means disclosed by the technical means, and the technical scheme also comprises the technical scheme formed by any combination of the technical characteristics. While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that various changes may be made in the embodiments without departing from the principles of the invention, and that such changes and modifications are intended to be included within the scope of the invention.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (3)
1. The active composite material for the lithium ion battery is characterized by comprising silicon micro-nano particles, graphite and graphene, wherein the composite material comprises the following components in percentage by mass: 20-40% of silicon micro-nano particles, 3-8% of graphene and the balance of graphite;
the preparation method of the active composite material comprises the following steps:
s1, carrying out weak oxidation treatment on graphite;
s2, mixing the graphite subjected to weak oxidation treatment with the silicon micro-nano particles, and carrying out high-speed ball milling in an argon atmosphere;
s3, performing medium-speed high-temperature ball milling in an argon atmosphere to obtain a silicon/graphite/graphene active composite material;
the step S1 of weak oxidation treatment specifically comprises the following steps: adding graphite into ice bath concentrated sulfuric acid, adding potassium permanganate, uniformly mixing, adding hydrogen peroxide and deionized water, reacting, washing with hydrochloric acid and deionized water, and drying in vacuum to obtain weakly oxidized graphite; the mass ratio of the graphite to the potassium permanganate is 1 (1.5-4.0);
the mass ratio of the graphite subjected to weak oxidation treatment to the silicon micro-nano particles in the step S2 is (2.5-4) to 1;
s2, setting the rotation speed of a ball milling tank in the high-speed ball milling to be 250-350rpm in self-transmission and 700-1000rpm in revolution, wherein the high-speed ball milling time is 2-3h;
s3, setting the rotation speed of a ball milling tank in the medium-speed high-temperature ball milling to be 150-250rpm in self-transmission and 300-500rpm in revolution; the ball milling time at medium speed is 15-18h;
and the temperature of the medium-speed high-temperature ball milling in the step S3 is 300-500 ℃.
2. The active composite material for the lithium ion battery according to claim 1, wherein the silicon micro-nano particles have a particle size of 60-200nm.
3. The active composite material for lithium ion batteries according to claim 1, characterized in that the vacuum drying temperature is 95-120 ℃ and the time is 8-15h.
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