CN111883761A - Silicon graphene composite lithium battery negative electrode material and preparation method thereof - Google Patents
Silicon graphene composite lithium battery negative electrode material and preparation method thereof Download PDFInfo
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a silicon graphene composite lithium battery cathode material and a preparation method thereof, wherein the cathode material comprises composite particles formed by graphene-silicon particles, a vertical graphene layer is attached to the surface of the silicon particles, the thickness of the vertical graphene layer is 1-100 nm, the height of the vertical graphene layer is 10-3000 nm, the particle size of the graphene-silicon composite particles is 30-5000nm, and the silicon graphene composite has the advantages of high conductivity, high specific surface area and the like and overcomes the problem of poor binding force between the conventional graphene sheet layer and a silicon substrate.
Description
Technical Field
The invention belongs to the field of lithium battery materials, and particularly relates to a silicon graphene composite lithium battery negative electrode material and a preparation method thereof.
Background
The lithium ion battery is the most widely applied energy storage battery in the current energy storage technology, the aim of improving the energy storage density of the lithium ion battery is pursued all over the world, and the improvement of the energy density of the lithium ion battery mainly depends on the development progress of positive and negative electrode materials of the lithium ion battery. Graphite negative electrode materials are generally adopted in the industry as negative electrode materials of lithium ion batteries, but the energy density of the graphite negative electrode materials is low (the theoretical specific capacity is 372 mAh/g). However, silicon is a lithium ion battery negative electrode material with the highest known specific capacity (theoretical specific capacity of 4200mAh/g), but because silicon has high lithium ion intercalation performance, a huge volume effect (> 300%) is generated, and the silicon electrode material is easily pulverized and peeled off from a current collector during charging and discharging, so that conductive contact between an active material and the active material and between the active material and the current collector is lost, and finally electrochemical performance is deteriorated and even fails.
Graphene is the thinnest and hardest nano material known in the world, is almost completely transparent, only absorbs 2.3% of visible light, has the resistivity of only about 10 & lt-6 & gtomega & cm, is lower than copper or silver, is a material with the smallest resistivity in the world, and has excellent mechanical properties, the Young modulus of the graphene is up to 1100GPa, and the breaking strength is 130 GPa. Therefore, the vertical graphene layer prepared on the surface of the silicon particle can remarkably improve the conductivity of the silicon particle, so that the lithium battery can be charged and discharged quickly, and the volume effect of the simple substance silicon particle in the application of the lithium battery can be relieved.
However, the graphene sheet layer grown by the general CVD method must be grown by a catalyst, and the commonly used catalyst includes common elements such as iron, cobalt, nickel, and copper …, even if the graphene grows on the surface of the catalyst, rather than directly on the surface of the silicon, the graphene sheet layer and the silicon are not well bonded, and on the other hand, the catalyst affects the electrochemical characteristics of the lithium battery, so that the subsequent application is limited.
CN110752363A discloses a preparation method of a composite negative electrode material, which comprises synthesis of graphene oxide, spray drying, and thermal reduction. The method processes two-dimensional graphene into a three-dimensional conductive network by a spray drying technology, and the three-dimensional conductive network can keep electrical contact with active silicon particles to maintain the stability of an electrode structure; silicon powder is wrapped in the inner cavity of the composite material, so that graphene can be prevented from being stacked, the flexible graphene layer can buffer the volume effect of silicon and absorb stress, and the wrapped composite material is obtained; the obtained composite material has high specific capacity and better cycle and rate capability. According to the method, the silicon particles are physically wrapped by directly using the graphene sheets, the silicon particles are wrapped by non-vertical graphene, a channel for lithium ions to be embedded into the silicon particles is blocked, the charging amount is influenced, and a contact ohmic resistor exists between the silicon particles and the graphene.
CN111430676A is a negative electrode material of a lithium ion battery, which has a core-shell structure, the material forming the core of the core-shell structure includes a silicon material and a solid electrolyte material, and the shell of the core-shell structure is formed by graphene. The silicon material comprises at least one of simple substance silicon and silicon oxide, the particle size of the silicon material is 0.01-5 microns, and the solid electrolyte material comprises at least one of an oxide-based solid electrolyte, a sulfide-based solid electrolyte and a polymer-based solid electrolyte. The negative electrode material ensures good ionic conductivity among silicon particles in the negative electrode material, thereby improving the exertion of silicon capacity and improving the rate capability. The material uses solid-state electrolysis to wrap silicon particles, so that expansion and contraction of the silicon particles during charging and discharging cannot be limited, and finally, the silicon particles are also physically wrapped by graphene sheets, and the non-vertical graphene wrapping blocks lithium ions from being embedded into channels of the silicon particles, so that the charging amount is influenced.
CN108598449A discloses a high performance hollow silicon carbon graphene ternary composite anode material, belongs to lithium ion battery anode material technical field, and includes simple substance silicon, simple substance carbon and graphene, the simple substance silicon is hollow silicon ball, the simple substance silicon and the simple substance carbon form carbon-coated hollow silicon, the carbon-coated hollow silicon is attached between graphene layers. According to the nano hollow silicon, a certain space is reserved for silicon volume expansion in the hollow structure, so that stress is in the direction of the sphere center when the silicon volume expansion occurs, nano silicon particles are not easy to break, the integrity of the particles and the integrity of electrodes in the circulation process are reserved, and a stable SEI film is formed. The cathode material is prepared by firstly manufacturing hollow silicon particles, and then physically wrapping the hollow silicon particles by the graphene sheets, and also belongs to non-vertical graphene wrapping, so that a channel for lithium ions to be embedded into the silicon particles is blocked, and the charging amount is influenced.
Disclosure of Invention
The invention aims to grow vertical graphene on the surface of a silicon particle to prepare a graphene-silicon composite particle, the particle is used as a lithium battery cathode material, has the advantages of high conductivity, high specific surface area and the like, and overcomes the problem of poor binding force between a graphene sheet layer and a silicon substrate in the prior art. Meanwhile, the volume effect of the simple substance silicon particles in the application of the lithium battery is relieved.
The invention relates to a silica graphene composite lithium battery cathode material, which is a composite particle consisting of graphene and silicon particles, and is characterized in that: the vertical graphene layer is attached to the surface of the silicon particle.
According to the lithium battery cathode material, the thickness of the vertical graphene layer is 1-100 nm, the height of the vertical graphene layer is 10-3000 nm, the particle size of the silicon particles is 10-5000nm, and the particle size of the graphene-silicon composite particles is 30-5000 nm.
On the other hand, the invention also provides a method for preparing the silicon graphene composite lithium battery cathode material, wherein the silicon graphene composite is a composite particle consisting of graphene and silicon particles, is prepared by adopting a PECVD method, and specifically comprises the following steps:
1) uniformly coating single-crystal micron silicon on a molybdenum metal substrate with the thickness of 40 multiplied by 40 mm;
2) placing the molybdenum metal substrate coated with the monocrystalline micron silicon on a carrying platform, and placing the carrying platform into a stainless steel vacuum cavity;
3) closing the stainless steel vacuum chamber door, starting the vacuum pump to vacuumize to 1.0 × 10-3torr；
4) Opening H2Valve H2Setting the gas flow rate to be 2000sccm, and setting the gas pressure in the vacuum cavity to be 3torr through the controller;
5) after the pressure in the cavity is stabilized at 3torr, a direct-current power switch is turned on, and the power of the direct-current power supply is set to be 0.1 KW;
6) after the plasma is stabilized, setting the pressure in the cavity to be 30torr, and setting the power of the direct current power supply to be 0.3 KW;
7) after the pressure in the cavity is stabilized at 30torr, CH is opened4Valve, CH4The gas setting flow rate is 500sccm, and the pressure in the vacuum cavity is set to be 60 torr;
8) after the pressure in the cavity is stabilized at 60torr, the gas flow is changed into H2:CH410:1, and setting the direct current electric power to 0.5 KW;
9) after the reaction is finished, the direct current power switch is closed, and H is closed2Valve, close CH4The valve is cooled along with the system after the controller for controlling the air pressure of the vacuum cavity is closed;
10) after the temperature is reduced to the room temperature, the vacuum pump is closed;
11) and opening a nitrogen valve, and opening a stainless steel vacuum cavity door to obtain the graphene-monocrystalline silicon composite particles.
In the method, in the step 1), the single-crystal micron silicon is uniformly and horizontally placed in parallel, and the carrier is arranged in the central area of the lower assembly of the plasma assembly in the cavity. The particle size of the obtained graphene-monocrystalline silicon composite particles is 30-5000 nm.
The technical scheme adopted for realizing the purpose of the invention is as follows: the graphene-silicon composite particles are prepared by a PECVD method, do not contain any catalyst such as iron, cobalt, nickel, copper … and the like, directly grow on the surfaces of silicon particles, and are formed by attaching vertical graphene layers on the surfaces of the silicon particles.
The method disclosed by the invention does not use any catalyst, ensures that the graphene directly grows on the surface of the silicon particles, and has excellent bonding force with the silicon particle substrate.
The invention has the advantages that: the vertical graphene sheet layers and the silicon particle substrate are tightly combined, and the high toughness and conductivity of the graphene can not be damaged, so that the material has high toughness and high conductivity, and the volume effect of the simple substance silicon particles in the application of the lithium battery is relieved.
According to the invention, the graphene-silicon composite particles are prepared by adopting a PECVD method, and the vertical graphene is directly grown on the surface of the silicon particles, so that the silicon particles and the graphene are good in electric conduction and firm in combination, and the three-dimensional conductive network structure is more stable when the silicon particles and the graphene are used. Thereby overcome prior art and carried out physics nature parcel to the silicon granule because of adopting the graphite alkene thin slice, formed non-vertical graphite alkene parcel, blockked the passageway that lithium ion imbedded the silicon granule to the defect of charge volume has been influenced.
Drawings
FIG. 1 is a schematic view of a high density Plasma Enhanced Chemical Vapor Deposition (PECVD) apparatus;
fig. 2 is a micrograph of the original silicon particles:
fig. 3 is a photomicrograph of the surface-grown vertical graphene of the silicon particles.
Detailed Description
The following examples are merely representative to further illustrate and understand the spirit of the present invention, but are not intended to limit the scope of the present invention in any way. In the specific implementation process, the graphene modified monocrystalline micron silicon electrode is prepared by taking commercial monocrystalline micron silicon as a raw material and adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) method. The electrode material has the advantages of high conductivity, large specific surface area, good stability, high electrochemical catalytic activity and the like.
The invention adopts PECVD method to prepare graphene-silicon composite particles, the schematic diagram of the PECVD) equipment is shown in figure 1, the equipment mainly comprises: the device comprises a main control device 1, a monocrystalline micron silicon raw material 2, valves 3 (such as a nitrogen valve, an H2 valve, a CH4 valve and the like), a stainless steel vacuum cavity 4, instrument sensors 5 (such as a vacuum gauge, a temperature sensor and the like), a plasma generation assembly 6 and the like, and the specific mechanisms are as follows:
The present invention will be further described with reference to the following examples.
EXAMPLE 1 preparation
In this embodiment, the preparation method of the graphene-modified single crystal micro silicon (graphene-silicon composite particles) includes the following steps:
1. a method of single crystal micron silicon processing comprising the steps of:
(1) single crystal micron silicon (silicon particles as shown in figure 2) was weighed at 100 mg.
(2) The weighed single crystal micron silicon was uniformly coated on a 40 x 40mm molybdenum metal substrate.
2. The preparation method of the graphene modified single crystal micron silicon comprises the following steps:
(1) and placing the metal substrate for placing the monocrystalline micron silicon on the carrying platform in a uniform horizontal parallel mode, and placing the metal carrying platform into a stainless steel vacuum cavity and the central area of a lower component of the plasma component.
(2) The stainless steel vacuum chamber door was closed and the vacuum pump was started to evacuate to 1.0X 10-3 torr.
(3) The H2 valve was opened, the H2 gas set at 2000sccm, and the gas pressure in the vacuum chamber was set to 3torr by the controller.
(4) After the pressure in the cavity is stabilized at 3torr, the DC power switch is turned on, and the power of the DC power supply is set at 0.1 KW.
(5) After the plasma is stabilized, the pressure in the cavity is set to be 30torr, and the power of the direct current power supply is set to be 0.3 KW.
(6) After the pressure in the cavity is stabilized at 30torr, the CH4 valve is opened, the CH4 gas is set to have a flow of 500sccm, and the pressure in the vacuum cavity is set to be 60 torr.
(7) After the pressure in the chamber stabilized at 60torr, the gas flow was modified to H2: CH4 to 10:1 and the dc power was set to 0.5 KW. The DC power supply has the following functions: and opening plasma, enhancing the decomposition of a gas precursor, heating the monocrystalline micron silicon, simultaneously reducing the reaction temperature, reacting for 5min, and preparing the graphene modified monocrystalline micron silicon by plasma enhanced chemical vapor deposition.
(8) And after the reaction is finished, closing the direct-current power switch, closing the H2 valve, closing the CH4 valve, closing the controller for controlling the air pressure of the vacuum cavity and then cooling the system.
(9) And after the temperature is reduced to the room temperature, the vacuum pump is closed.
(10) And opening a nitrogen valve, and opening a cavity door of the stainless steel vacuum cavity to obtain the graphene modified monocrystalline micron silicon sample (namely graphene-silicon composite particles).
(11) In the embodiment, the graphene in the obtained modified monocrystalline silicon is uniformly distributed, and the aggregation phenomenon does not occur.
Microscopic observation shows that the vertical graphene grows on the surface of the silicon particle, as shown in fig. 3.
Example 2 graphene-silicon composite particle-related performance testing of example 1
1) Particle size: the particle size range of the graphene-silicon composite particles is 30-5000 nm.
2) The thickness of the vertical graphene layer is 1-100 nm, the height is 10-3000 nm,
3) the initial charge efficiency of the lithium ion battery prepared by using the commercial monocrystalline micron silicon as the negative electrode in example 1 is 40% at 0.2A/g, and the initial charge efficiency of the lithium ion battery prepared by using the graphene modified monocrystalline micron silicon prepared in example 1, namely the graphene-silicon composite particles as the negative electrode in example 1 at 0.2A/g is as high as 83.8%, which is more than twice as high as that of the commercial monocrystalline micron silicon. The graphene modified monocrystalline micron silicon is far better than commercial monocrystalline micron silicon in specific surface area and conductivity, and the corresponding battery performance can be improved. Meanwhile, the service life of the prepared battery is far longer than that of a commercial monocrystalline micron silicon battery, the charge-discharge cycle performance and the service life of the battery in the lithium ion battery are also longer than those of the battery prepared from monocrystalline micron silicon, and the industrial development of the lithium ion battery can be promoted by adapting to the application requirements of the lithium ion battery.
Through a charge and discharge amount test, the graphene-silicon composite particles are used as a lithium battery cathode, then the charge amount of the battery is tested, and the battery is compared with a silicon electrode lithium battery without wrapping graphene and a non-vertical graphene-silicon particle lithium battery, and the lithium battery is tested, and the result shows that the charge and discharge amount of the graphene-silicon composite particle lithium battery is more than one time than that of the silicon particle lithium battery without long graphene, and the charge and discharge amount of the graphene-silicon composite particle lithium battery is also more than two thirds than that of the non-vertical graphene-silicon particle lithium battery such as a CN110752363A lithium battery.
Claims (8)
1. A silica graphene composite lithium battery negative electrode material is a composite particle composed of graphene-silicon particles, and is characterized in that: the vertical graphene layer is attached to the surface of the silicon particle.
2. The negative electrode material for a lithium battery as claimed in claim 1, wherein the vertical graphene layer has a thickness of 1 to 100nm and a height of 10 to 3000 nm.
3. The negative electrode material for lithium batteries as claimed in claim 1, wherein the silicon particles have a particle size of 10 to 5000 nm.
4. The negative electrode material for lithium batteries as claimed in claim 1, wherein the particle diameter of the graphene-silicon composite particles is 30to 5000 nm.
5. The method for preparing the silicon graphene composite lithium battery cathode material is characterized in that the silicon graphene composite is a composite particle consisting of graphene and silicon particles, is prepared by adopting a PECVD method, and specifically comprises the following steps:
1) uniformly coating single-crystal micron silicon on a molybdenum metal substrate with the thickness of 40 multiplied by 40 mm;
2) placing the molybdenum metal substrate coated with the monocrystalline micron silicon on a carrying platform, and placing the carrying platform into a stainless steel vacuum cavity;
3) closing the stainless steel vacuum chamber door, starting the vacuum pump to vacuumize to 1.0 × 10-3torr；
4) Opening H2Valve H2Setting the gas flow rate to be 2000sccm, and setting the gas pressure in the vacuum cavity to be 3torr through the controller;
5) after the pressure in the cavity is stabilized at 3torr, a direct-current power switch is turned on, and the power of the direct-current power supply is set to be 0.1 KW;
6) after the plasma is stabilized, setting the pressure in the cavity to be 30torr, and setting the power of the direct current power supply to be 0.3 KW;
7) after the pressure in the cavity is stabilized at 30torr, CH is opened4Valve, CH4The gas setting flow rate is 500sccm, and the pressure in the vacuum cavity is set to be 60 torr;
8) after the pressure in the cavity is stabilized at 60torr, the gas flow is changed into H2:CH410:1, and setting the direct current electric power to 0.5 KW;
9) after the reaction is finished, the direct current power switch is closed, and H is closed2Valve, close CH4The valve is cooled along with the system after the controller for controlling the air pressure of the vacuum cavity is closed;
10) after the temperature is reduced to the room temperature, the vacuum pump is closed;
11) and opening a nitrogen valve, and opening a stainless steel vacuum cavity door to obtain the graphene-monocrystalline silicon composite particles.
6. The method of claim 5, wherein in step 1), the single crystal silicon micron is disposed in a uniform horizontal parallel arrangement.
7. The method of claim 5, wherein in step 1), the carrier is positioned in a center region of a lower assembly of the plasma assembly within the chamber.
8. The method of claim 5, wherein the obtained graphene-single crystal silicon composite particles have a particle size of 30-5000 nm.
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