CN105870427B - Lithium ion battery negative electrode material, preparation method thereof and lithium ion battery - Google Patents
Lithium ion battery negative electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
The invention provides a lithium ion battery cathode material, which comprises a core and a shell, wherein a hollow layer is arranged between the core and the shell; the shell is made of carbon material, and the inner core is made of porous silicon material. The core and the hollow layer act synergistically, so that huge volume changes of silicon particles in the charging and discharging process can be accommodated, the shell can buffer the volume changes, the stress is reduced, the structure of the silicon-carbon composite material is stabilized, the circulation stability of the electrode is improved, the contact between an active substance and an electrolyte is reduced, a stable solid electrolyte interface film (SEI film) is obtained, the coulombic efficiency of the electrode is improved, the agglomeration of nano particles can be prevented, and the conductivity of the electrode is improved. The cathode material prepared by adopting the core-shell structure has higher specific capacity, and meanwhile, the lithium ion battery prepared by the cathode material has better electrochemical cycle performance. Moreover, the preparation method disclosed by the invention is simple and feasible, and is beneficial to large-scale production.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery cathode material, a preparation method thereof and a lithium ion battery.
Background
In the research of the negative electrode material of the lithium ion battery, the silicon-based negative electrode material attracts attention with the advantages of huge lithium storage capacity (4200mAh/g), a discharge platform slightly higher than that of a carbon material, abundant storage in the earth crust and the like. However, during charge and discharge, the lithium deintercalation reaction of silicon is accompanied by a volume change of 310%, and it is very easy to cause cracking of an electrode and falling-off of an active material, thereby causing rapid deterioration of cycle performance of the electrode.
One of the methods for solving the above problems is to synthesize a silicon-based composite to buffer the volume expansion of the electrode and improve the cycle stability of the electrode. The carbon material has the advantages of flexibility, good electronic conductivity, smaller density, smaller volume expansion, proper lithium intercalation capacity and the like, so that the silicon-carbon composite material becomes the optimal choice of the silicon-based negative electrode material.
For the silicon-carbon composite material, reasonable structure design is the key for obtaining excellent electrochemical performance, and a core-shell structure is one of the structures for obtaining excellent electrochemical performance. In the prior art, in the prepared silicon-carbon composite material with the core-shell structure, the inner core is usually granular silicon material. When the obtained core structure is porous silicon, the carbon layer in the prepared core-shell structure is coated on all surfaces of the silicon material, including the surface of the inner hole wall of the silicon material, so as to form filling type coating. The preparation of the silicon-carbon composite materials with the two core-shell structures generally adopts a template method, such as: after obtaining a carbon shell using silicon dioxide as a sacrificial template, the silicon dioxide is removed to obtain a silicon-carbon composite material with a core-shell structure (see n.liu, z.lu, j.zhao, m.t.mcdowell, h.w.lee, w.zhao and y.cui, Nature Nanotechnology,2014,9, 187; z.d.lu, n.liu, h.w.lee, j.zhao, w.y.li, y.z.li and y.cui, naacs no,2015,9, 2540; n.liu, h.wu, m.t.mcdowell, y.yao, c.m.wang and y.cui, Nano Letters,2012,12, 3315; h.kim, b.han, j.choo, angew.m.int.em, e.10152. (54)). The core-shell structure silicon-carbon composite material prepared by the method can effectively relieve the problems caused by silicon volume expansion, and has good cycle performance and high specific capacity. However, the preparation method is complex to operate, less template materials are available, synthesis is difficult, highly corrosive hydrofluoric acid is required for removing the template, the cost is high, the yield is low, and the core-shell structure is easily damaged in the template removing process. Obviously, this approach significantly limits the commercial application of core-shell structures. How to adopt a simple method to prepare the core-shell structure silicon-carbon composite material with excellent performance on a large scale still remains an urgent problem to be solved.
Disclosure of Invention
in view of the above, the technical problem to be solved by the present invention is to provide a lithium ion battery negative electrode material, a preparation method thereof, and a lithium ion battery, wherein the preparation method is simple and easy, and is beneficial to large-scale production, and the prepared negative electrode material has a high specific capacity, and meanwhile, the lithium ion battery prepared from the negative electrode material has a good electrochemical cycle performance.
The invention provides a lithium ion battery cathode material, which comprises a core and a shell, wherein a hollow layer is arranged between the core and the shell;
The shell is made of carbon material, and the inner core is made of porous silicon material.
Preferably, the thickness of the outer shell is 100nm to 5 μm.
preferably, the particle size of the inner core is 500 nm-10 μm, and the pore diameter of the inner core is 10 nm-100 nm.
The invention provides a preparation method of the lithium ion battery cathode material, which comprises the following steps:
A) Performing alkali treatment on calcium silicide to obtain pretreated calcium silicide;
B) Heating the pretreated calcium silicide, and introducing a gaseous hydrocarbon compound to carry out chemical vapor deposition to obtain a chemical vapor deposition product;
C) and carrying out acid washing treatment on the chemical vapor deposition product to obtain the lithium ion battery cathode material.
Preferably, the particle size of the pretreated calcium silicide is 500nm to 10 μm.
Preferably, in the step B), the heating of the pretreated calcium silicide is specifically: and (3) placing the pretreated calcium silicide in a high-temperature tube furnace, and heating in the presence of protective gas.
Preferably, the temperature of the chemical vapor deposition is 600-1000 ℃; the time of the chemical vapor deposition is 10 min-120 min.
Preferably, the acid solution used in the acid washing treatment is one or more selected from hydrochloric acid, nitric acid, hydrobromic acid and hydroiodic acid.
Preferably, the acid solution is 5 to 36 mass percent.
The invention also provides a lithium ion battery which comprises an anode, a cathode, a diaphragm and electrolyte, wherein the cathode comprises the lithium ion battery cathode material or the lithium ion battery cathode material prepared by the preparation method.
The invention provides a lithium ion battery cathode material, which comprises a core and a shell, wherein a hollow layer is arranged between the core and the shell; the shell is made of carbon material, and the inner core is made of porous silicon material. A hollow layer exists between the porous silicon material of the inner core and the carbon material of the shell, and the inner core and the hollow layer have synergistic effect, so that the huge volume change of silicon particles in the charge and discharge process can be accommodated, and the key is very important for obtaining good cycle performance of the negative electrode material of the lithium ion battery. The shell can buffer the volume change, reduce the stress, stabilize the structure of the silicon-carbon composite material, improve the cycling stability of the electrode, reduce the contact between active substances and electrolyte, obtain a stable solid electrolyte interface film (SEI film), improve the coulombic efficiency of the electrode, prevent the agglomeration of nano particles and improve the conductivity of the electrode. The cathode material prepared by adopting the core-shell structure has higher specific capacity, and meanwhile, the lithium ion battery prepared by the cathode material has better electrochemical cycle performance.
The invention also provides a preparation method of the lithium ion battery cathode material, which comprises the following steps: A) performing alkali treatment on calcium silicide to obtain pretreated calcium silicide; B) heating the pretreated calcium silicide, and introducing a gaseous hydrocarbon compound to carry out chemical vapor deposition to obtain a chemical vapor deposition product; C) and carrying out acid washing treatment on the chemical vapor deposition product to obtain the lithium ion battery cathode material. The existing template method is complex in operation, available template materials are few and difficult to synthesize, highly corrosive and highly toxic hydrofluoric acid is needed for removing the template, the cost is high, the yield is low, and meanwhile, the core-shell structure is easy to damage in the template removing process. Obviously, this approach significantly limits the commercial application of core-shell structures. Compared with the prior art, the preparation method disclosed by the invention is simple and feasible, is beneficial to large-scale production, and the prepared negative electrode material has higher specific capacity, and meanwhile, the lithium ion battery prepared from the negative electrode material has better electrochemical cycle performance.
Drawings
Fig. 1 is an SEM image of a negative electrode material prepared in example 1 of the present invention;
fig. 2 is an XRD pattern of the anode material prepared in example 1 of the present invention;
FIG. 3 is a first charge-discharge curve diagram of a lithium ion battery prepared in example 1 of the present invention;
FIG. 4 is a graph showing the cycle profile of a lithium ion battery prepared in example 1 of the present invention;
Fig. 5 is a charge-discharge specific capacity curve diagram of the lithium ion battery prepared in example 1 of the present invention at different multiplying powers.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a lithium ion battery cathode material, which comprises a core and a shell, wherein a hollow layer is arranged between the core and the shell;
The shell is made of carbon material, and the inner core is made of porous silicon material.
the lithium ion battery cathode material disclosed by the invention is of a core-shell structure, wherein the core-shell structure contains a hollow layer, and a shell is separated from an inner core; the shell is made of carbon material, and the inner core is made of porous silicon material. No carbon material adheres to the pore walls of the porous silicon material.
the carbon material of the present invention is obtained by chemical vapor deposition of gaseous hydrocarbon compounds. The gaseous hydrocarbon compound is not particularly limited in the present invention, and it is sufficient to use a gaseous hydrocarbon compound known to those skilled in the art, and one or more of methane, ethylene and acetylene are preferably used in the present invention.
The particle size of the lithium ion battery negative electrode material disclosed by the invention is preferably 1-20 μm, and more preferably 3-10 μm; the thickness of the shell is 100 nm-5 μm, preferably 1 μm-3 μm; the particle size of the inner core is 500 nm-10 μm, preferably 1 μm-5 μm; the pore diameter of the inner core is 10 nm-100 nm, preferably 20 nm-50 nm.
The invention discloses a lithium ion battery cathode material with a core-shell structure, which comprises the following components in parts by weight: the carbon material coating layer is arranged outside the whole inner core, and no carbon material is attached to the surface of the inner hole wall of the inner core, so that the inner core is non-filled. A hollow layer exists between the porous silicon material of the inner core and the carbon material of the shell, and the inner core and the hollow layer have synergistic effect, so that the huge volume change of silicon particles in the charge and discharge process can be accommodated, and the key is very important for obtaining good cycle performance of the negative electrode material of the lithium ion battery. The shell can buffer the volume change, reduce the stress, stabilize the structure of the silicon-carbon composite material, improve the circulating stability of the electrode, reduce the contact of active substances and electrolyte, obtain a stable SEI film, improve the coulombic efficiency of the electrode, prevent the agglomeration of nano particles and improve the conductivity of the electrode. The cathode material prepared by adopting the core-shell structure has higher specific capacity, and meanwhile, the lithium ion battery prepared by the cathode material has better electrochemical cycle performance.
the invention provides a preparation method of the lithium ion battery cathode material, which comprises the following steps:
A) performing alkali treatment on calcium silicide to obtain pretreated calcium silicide;
B) heating the pretreated calcium silicide, and introducing a gaseous hydrocarbon compound to carry out chemical vapor deposition to obtain a chemical vapor deposition product;
C) And carrying out acid washing treatment on the chemical vapor deposition product to obtain the lithium ion battery cathode material.
the calcium silicide is preferably ball-milled calcium silicide obtained by ball-milling calcium silicide particles, and more preferably, the calcium silicide particles are ball-milled in a protective atmosphere. The calcium silicide particles used in the present invention are not particularly limited, and those known to those skilled in the art can be used. The calcium silicide particles preferably used in the present invention are purchased from national pharmaceutical group chemical agents limited (Ca ≈ 30%). The particle diameter of the calcium silicide particles is preferably 1 μm to 100. mu.m. The method of ball milling is not particularly limited in the present invention, and a ball milling method known to those skilled in the art may be used. The present invention preferably employs high energy mechanical ball milling. The rotation speed of the ball milling is preferably 300-600 rpm, and more preferably 350-450 rpm; the ball milling time is preferably 6-10 h, and more preferably 7-9 h. The protective gas used in the protective atmosphere of the present invention is not particularly limited, and any protective gas known to those skilled in the art may be used. Nitrogen or argon is preferably used in the present invention.
After the calcium silicide is obtained, it is subjected to alkali treatment, and the method of alkali treatment is not particularly limited in the present invention, and an alkali treatment method known to those skilled in the art may be employed, and it is preferable in the present invention to stir the calcium silicide in an alkaline solution. The alkaline solution used in the present invention is not particularly limited, and those known to those skilled in the art can be used. The invention preferably adopts one or more of sodium hydroxide solution, potassium hydroxide solution and lithium hydroxide solution. The concentration of the alkaline solution is preferably 0.1-5 mol/L, and more preferably 1-3 mol/L. The solvent of the alkaline solution is preferably water. The mass ratio of the solute of the alkaline solution to the calcium silicide particles is preferably 2-6: 1 to 4, more preferably 3 to 5: 2 to 3.
The time of the alkali treatment is preferably 10-48 h, and more preferably 16-24 h. The temperature of the alkali treatment is preferably 15-35 ℃, and more preferably 20-30 ℃.
The particle size of the pretreated calcium silicide obtained above is preferably 500nm to 10 μm, more preferably 1 μm to 5 μm.
And then heating the pretreated calcium silicide, specifically: and (3) placing the pretreated calcium silicide in a high-temperature tube furnace, and heating in the presence of protective gas. The high-temperature tube furnace of the present invention is not particularly limited, and a high-temperature tube furnace known to those skilled in the art may be used. The invention preferably employs a quartz tube furnace. The shielding gas used in the present invention is not particularly limited, and any shielding gas known to those skilled in the art may be used. Nitrogen or argon is preferably used in the present invention. The gas flow of the protective gas is preferably 200scc min < -1 >, and after heating, the heating rate is preferably 5 ℃ min < -1 > to 15 ℃ min < -1 >, and more preferably 10 ℃ min < -1 >.
Heating to the temperature of chemical vapor deposition, and introducing gaseous hydrocarbon compounds to carry out chemical vapor deposition to obtain a chemical vapor deposition product. The method of chemical vapor deposition is not particularly limited in the present invention, and chemical vapor deposition methods known to those skilled in the art may be used, and atmospheric vapor deposition is preferred in the present invention. The gaseous hydrocarbon compound is not particularly limited in the present invention, and it is sufficient to use a gaseous hydrocarbon compound known to those skilled in the art, and one or more of methane, ethylene and acetylene are preferably used in the present invention. The flow rate of the gaseous hydrocarbon compound is preferably 100scc min < -1 > to 300scc min < -1 >, and more preferably 150scc min < -1 > to 250scc min < -1 >. The volume mass ratio of the gaseous hydrocarbon compound to the pretreated calcium silicide is preferably 1L to 36L: 1g to 10g, more preferably 6.75L to 22.5L: 3g to 8 g.
The time for introducing the gaseous hydrocarbon compound is the time for chemical vapor deposition, and is preferably 10min to 120min, more preferably 45min to 90min, and even more preferably 45 min; the temperature of the chemical vapor deposition is preferably 600 ℃ to 1000 ℃, and more preferably 800 ℃ to 900 ℃.
After the chemical vapor deposition is finished, the obtained product is preferably cooled to room temperature along with a high-temperature tube furnace to obtain a chemical vapor deposition product.
And carrying out acid washing treatment on the chemical vapor deposition product to obtain the lithium ion battery cathode material.
specifically, the chemical vapor deposition product is stirred in an acid solution for reaction to obtain the lithium ion battery cathode material.
The acid washing treatment is used for removing calcium carbide to obtain the core porous silicon material. The acid solution adopted in the acid cleaning treatment is one or more selected from hydrochloric acid, nitric acid, hydrobromic acid and hydroiodic acid; the mass percent of the acid solution is preferably 5 to 36%, and more preferably 15 to 20%. The volume mass ratio of the acid solution to the chemical vapor deposition product is preferably 100 mL-300 mL: 3g to 12g, more preferably 150mL to 250 mL: 5g to 10 g.
The acid washing time, i.e., the time for stirring reaction in the acid solution, is preferably 2 to 12 hours, and more preferably 3 to 6 hours. After the stirring reaction in the acid solution, preferably, the product after the reaction is filtered, washed and dried to obtain the lithium ion battery cathode material.
The invention also provides a lithium ion battery which comprises an anode, a cathode, a diaphragm and electrolyte, wherein the cathode comprises the lithium ion battery cathode material or the lithium ion battery cathode material prepared by the preparation method.
The invention has no special limitation to the types of the anode, the diaphragm and the electrolyte, for example, the anode can adopt a lithium sheet; the diaphragm can adopt a polypropylene microporous membrane; the electrolyte may be a mixture of Ethylene Carbonate (EC) and dimethyl carbonate (DMC). Specifically, the lithium ion battery negative electrode material is mixed with a binder (styrene butadiene rubber (SBR): sodium carboxymethyl cellulose (CMC): 3: 7 mass ratio) and a conductive agent Super P according to a ratio of 80: 10: 10, adding a proper amount of water as a dispersing agent to prepare slurry, then uniformly coating the slurry on a copper foil current collector, and preparing a negative plate through vacuum drying and rolling; a simulated battery is assembled in a glove box under the protection of argon by using metal lithium as a counter electrode, 1mol/L mixed solvent of LiPF6 (EC: DMC is 1:1 volume ratio) as electrolyte and a polypropylene microporous membrane (Celgard 2400) as a diaphragm.
The obtained simulated battery is subjected to a constant-current charge and discharge experiment, the cycle performance of the lithium ion battery is tested, the charge and discharge voltage is limited to 0.001-1.5 volts, and the charge and discharge current density is 150 mA/g. The electrochemical performance of the cell was tested using a Land tester (Wuhanxinnuo electronics Co., Ltd.) at room temperature. Experimental results show that the first discharge specific capacity of the lithium ion battery provided by the invention is not lower than 1254mAh/g, after the lithium ion battery is charged and discharged for 100 times in a circulating manner, the capacity retention rate is not lower than 80.3%, the coulombic efficiency is not lower than 99.4%, and the lithium ion battery has better circulating performance.
Meanwhile, the cycle performance of the obtained lithium ion battery under different multiplying powers is also examined, and experimental results show that the lithium ion battery provided by the invention has higher specific capacity under 0.1C, 0.2C, 0.5C, 1C and 2C, is still not less than 650mAh/g after being cycled for 50 times under 2C, and has better multiplying power performance.
The invention provides a lithium ion battery cathode material, which comprises a core and a shell, wherein a hollow layer is arranged between the core and the shell; the shell is made of carbon material, and the inner core is made of porous silicon material. The core-shell structure disclosed by the invention is characterized in that the carbon material wrapping layer is arranged outside the whole inner core, does not comprise the surface of the inner hole wall of the inner core, and is non-filling wrapping. A hollow layer exists between the porous silicon material of the inner core and the carbon material of the shell, and the inner core and the hollow layer have synergistic effect, so that the huge volume change of silicon particles in the charge and discharge process can be accommodated, and the key is very important for obtaining good cycle performance of the negative electrode material of the lithium ion battery. The shell can buffer the volume change, reduce the stress, stabilize the structure of the silicon-carbon composite material, improve the circulating stability of the electrode, reduce the contact of active substances and electrolyte, obtain a stable SEI film, improve the coulombic efficiency of the electrode, prevent the agglomeration of nano particles and improve the conductivity of the electrode. The cathode material prepared by adopting the core-shell structure has higher specific capacity, and meanwhile, the lithium ion battery prepared by the cathode material has better electrochemical cycle performance. Meanwhile, the preparation method disclosed by the invention is simple and feasible, and is beneficial to large-scale production. Experimental results show that under the conditions that the charging and discharging voltage is 0.001-1.5V and the charging and discharging current density is 150mA/g, the initial discharging specific capacity of the lithium ion battery provided by the invention is not lower than 1254mAh/g, after 100 times of circulating charging and discharging, the capacity retention rate is not lower than 80.3%, the coulombic efficiency is not lower than 99.4%, and the lithium ion battery has better circulating performance.
In order to further illustrate the present invention, the following will describe in detail a lithium ion battery anode material, a preparation method thereof and a lithium ion battery provided by the present invention with reference to the examples, but the present invention should not be construed as limiting the scope of the present invention.
Example 1
Placing calcium silicide particles with the calcium content of 30% in a ball milling tank, adding absolute ethyl alcohol as a ball milling medium, and carrying out high-energy mechanical ball milling for 8 hours at the rotating speed of 400rpm under the protection of argon atmosphere to obtain the low-particle-size calcium silicide slurry.
Adding the obtained low-particle-size calcium silicide slurry into 2mol/L sodium hydroxide aqueous solution, stirring and reacting for 20h at 25 ℃, then filtering and drying in vacuum to obtain pre-treated calcium silicide with the particle size of 3 mu m, wherein the mass ratio of sodium hydroxide to calcium silicide particles is 8: 5.
Placing pretreated calcium silicide in a quartz tube furnace, heating in the argon atmosphere, controlling the flow of argon to be 200scc min < -1 >, controlling the heating rate to be 10 ℃ min < -1 > after heating, stopping heating and preserving heat after heating to 900 ℃, introducing ethylene gas, controlling the flow to be 200scc min < -1 >, stopping introducing ethylene gas after 60min, cooling the obtained product to room temperature along with the furnace, and obtaining a chemical vapor deposition product, wherein the volume mass ratio of the ethylene gas to the pretreated calcium silicide is 12L: 8 g.
Adding the chemical vapor deposition product into hydrochloric acid with the mass fraction of 20%, stirring and reacting for 4h at room temperature, then filtering, washing for many times to be neutral, and drying the product to obtain the lithium ion battery negative electrode material, wherein the volume mass ratio of the hydrochloric acid to the chemical vapor deposition product is 200 mL: 10 g.
Scanning electron microscope scanning analysis is carried out on the obtained lithium ion battery negative electrode material, the result is shown in figure 1, figure 1 is an SEM image of the lithium ion battery negative electrode material prepared in the embodiment 1 of the invention, and as can be seen from figure 1, the core porous silicon material, the shell carbon material and the hollow layer between the core porous silicon material and the shell carbon material form the core-shell structure composite material with the grain size of 1-20 microns.
The obtained lithium ion battery negative electrode material was analyzed by an X-ray diffractometer, and an XRD pattern of the negative electrode material in example 1 of the present invention was obtained, as shown in fig. 2. As can be seen from fig. 2, the diffraction peak of the prepared lithium ion battery negative electrode material is the corresponding peak of silicon.
The obtained lithium ion battery negative electrode material is subjected to particle size D50 and specific surface area tests, and the test results are as follows: the median particle diameter D50 of the lithium ion battery negative electrode material is 5 μm, and the specific surface area is 5.4m 2/g.
According to the invention, the lithium ion battery negative electrode material, a binder (SBR: CMC: 3: 7 mass ratio) and a conductive agent Super P are mixed according to a proportion of 80: 10: 10, adding a proper amount of water as a dispersing agent to prepare slurry, then uniformly coating the slurry on a copper foil current collector, and preparing a negative plate through vacuum drying and rolling; a simulated battery is assembled in a glove box under the protection of argon by using metal lithium as a counter electrode, 1mol/L mixed solvent of LiPF6 (EC: DMC is 1:1 volume ratio) as electrolyte and a polypropylene microporous membrane (Celgard 2400) as a diaphragm. Performing constant-current charge and discharge test on the assembled analog battery on a Land tester (Wuhanxinnuo electronic Co., Ltd.), wherein the charge and discharge voltage interval is 0.001-1.5V, the charge and discharge current density is 150mA g-1, and the first charge and discharge curve is obtained and is shown in figure 3; the cycle performance curve is shown in fig. 4.
The experimental result shows that the first discharge specific capacity of the lithium ion battery provided by the invention is 1527mAh/g, and the first coulombic efficiency is 80.7%; after the charge and the discharge are cycled for 100 times, the capacity retention rate is 90.1%, the coulombic efficiency is 99.9%, and the cycle performance is better.
Meanwhile, the charge-discharge cycle performance of the obtained lithium ion battery under different multiplying powers is also examined, as shown in fig. 5. Experimental results show that the lithium ion battery provided by the invention has high specific capacity under 0.1C, 0.2C, 0.5C, 1C and 2C, is still not less than 650mAh/g after 2C circulation for 50 times, and has good rate capability.
Example 2
Placing calcium silicide particles with the calcium content of 30% in a ball milling tank, adding absolute ethyl alcohol as a ball milling medium, and carrying out high-energy mechanical ball milling for 8 hours at the rotating speed of 400rpm under the protection of argon atmosphere to obtain the low-particle-size calcium silicide slurry.
Adding the obtained low-particle-size calcium silicide slurry into 2mol/L sodium hydroxide aqueous solution, stirring and reacting for 20h at 25 ℃, then filtering and drying in vacuum to obtain pre-treated calcium silicide with the particle size of 3 mu m, wherein the mass ratio of sodium hydroxide to calcium silicide particles is 8: 5.
placing pretreated calcium silicide in a quartz tube furnace, heating in the argon atmosphere, controlling the flow of argon to be 200scc min < -1 >, controlling the heating rate to be 10 ℃ min < -1 > after heating, stopping heating and preserving heat after heating to 800 ℃, introducing ethylene gas, controlling the flow to be 200scc min < -1 >, stopping introducing ethylene gas after 60min, cooling the obtained product to room temperature along with the furnace, and obtaining a chemical vapor deposition product, wherein the volume mass ratio of the ethylene gas to the pretreated calcium silicide is 12L: 8 g.
adding the chemical vapor deposition product into hydrochloric acid with the mass fraction of 20%, stirring and reacting for 4h at room temperature, then filtering, washing for many times to be neutral, and drying the product to obtain the lithium ion battery negative electrode material, wherein the volume mass ratio of the hydrochloric acid to the chemical vapor deposition product is 200 mL: 10 g.
The obtained lithium ion battery negative electrode material is subjected to particle size D50 and specific surface area tests, and the test results are as follows: the median particle diameter D50 of the lithium ion battery negative electrode material is 3 μm, and the specific surface area is 5.4m 2/g.
The invention relates to a lithium ion battery cathode material, a binder (styrene butadiene rubber (SBR): sodium carboxymethyl cellulose (CMC): 3: 7 mass ratio) and a conductive agent Super P, wherein the weight ratio of the Styrene Butadiene Rubber (SBR): sodium carboxymethyl cellulose (CMC): 3: 7) to the conductive agent Super P is as follows that 80: 10: 10, adding a proper amount of water as a dispersing agent to prepare slurry, then uniformly coating the slurry on a copper foil current collector, and preparing a negative plate through vacuum drying and rolling; a simulated battery is assembled in a glove box under the protection of argon by using metal lithium as a counter electrode, 1mol/L mixed solvent of LiPF6 (EC: DMC is 1:1 volume ratio) as electrolyte and a polypropylene microporous membrane (Celgard 2400) as a diaphragm. And (3) carrying out constant-current charge and discharge test on the assembled analog battery on a Land tester (Wuhanxinnuo electronics Co., Ltd.), wherein the current density of charge and discharge is 150mA g-1, and the charge and discharge voltage interval is 0.001-1.5V.
The experimental result shows that the first discharge specific capacity of the lithium ion battery provided by the invention is 1254mAh/g, and the first coulombic efficiency is 76.2%; after the charge and the discharge are cycled for 100 times, the capacity retention rate is 87.6%, the coulombic efficiency is 99.6%, and the cycle performance is better.
Example 3
Placing calcium silicide particles with the calcium content of 30% in a ball milling tank, adding absolute ethyl alcohol as a ball milling medium, and mechanically milling for 10 hours at the rotating speed of 400rpm under the protection of argon atmosphere to obtain the low-particle-size calcium silicide slurry.
Adding the obtained low-particle-size calcium silicide slurry into 5mol/L sodium hydroxide aqueous solution, stirring and reacting for 35h at 15 ℃, then filtering and drying in vacuum to obtain pre-treated calcium silicide with the particle size of 2 mu m, wherein the mass ratio of sodium hydroxide to calcium silicide particles is 1: 1.
Placing pretreated calcium silicide in a quartz tube furnace, heating in the argon atmosphere, controlling the flow of argon to be 200scc min < -1 >, controlling the heating rate to be 15 ℃ min < -1 > after heating, stopping heating and preserving heat after heating to 1000 ℃, introducing ethylene gas, controlling the flow to be 200scc min < -1 >, stopping introducing ethylene gas after 25min, cooling the obtained product to room temperature along with the furnace, and obtaining a chemical vapor deposition product, wherein the volume mass ratio of the ethylene gas to the pretreated calcium silicide is 5L: 6 g.
Adding the chemical vapor deposition product into hydrochloric acid with the mass fraction of 10%, stirring and reacting for 8h at room temperature, then filtering, washing for many times to be neutral, and drying the product to obtain the lithium ion battery negative electrode material, wherein the volume mass ratio of the hydrochloric acid to the chemical vapor deposition product is 150 mL: 5g of the total weight.
The obtained lithium ion battery negative electrode material is subjected to particle size D50 and specific surface area tests, and the test results are as follows: the median particle diameter D50 of the lithium ion battery negative electrode material is 8 μm, and the specific surface area is 5.4m 2/g.
The invention relates to a lithium ion battery cathode material, a binder (styrene butadiene rubber (SBR): sodium carboxymethyl cellulose (CMC): 3: 7 mass ratio) and a conductive agent Super P, wherein the weight ratio of the Styrene Butadiene Rubber (SBR): sodium carboxymethyl cellulose (CMC): 3: 7) to the conductive agent Super P is as follows that 80: 10: 10, adding a proper amount of water as a dispersing agent to prepare slurry, then uniformly coating the slurry on a copper foil current collector, and preparing a negative plate through vacuum drying and rolling; a simulated battery is assembled in a glove box under the protection of argon by using metal lithium as a counter electrode, 1mol/L mixed solvent of LiPF6 (EC: DMC is 1:1 volume ratio) as electrolyte and a polypropylene microporous membrane (Celgard 2400) as a diaphragm. And (3) carrying out constant-current charge and discharge test on the assembled analog battery on a Land tester (Wuhanxinnuo electronics Co., Ltd.), wherein the current density of charge and discharge is 150mA g-1, and the charge and discharge voltage interval is 0.001-1.5V.
Experiment results show that the first discharge specific capacity of the lithium ion battery provided by the invention is 1467mAh/g, and the first coulombic efficiency is 79.5%; after the charge and the discharge are cycled for 100 times, the capacity retention rate is 80.3%, the coulombic efficiency is 99.4%, and the cycle performance is better.
example 4
Placing calcium silicide particles with the calcium content of 30% in a ball milling tank, adding absolute ethyl alcohol as a ball milling medium, and carrying out high-energy mechanical ball milling for 8 hours at the rotating speed of 400rpm under the protection of argon atmosphere to obtain the low-particle-size calcium silicide slurry.
Adding the obtained low-particle-size calcium silicide slurry into 2mol/L sodium hydroxide aqueous solution, stirring and reacting for 20h at 25 ℃, then filtering and drying in vacuum to obtain pre-treated calcium silicide with the particle size of 3 mu m, wherein the mass ratio of sodium hydroxide to calcium silicide particles is 3: 1.
Placing pretreated calcium silicide in a quartz tube furnace, heating in the argon atmosphere, controlling the flow of argon to be 200scc min < -1 >, controlling the heating rate to be 10 ℃ min < -1 > after heating, stopping heating and preserving heat after heating to 900 ℃, introducing ethylene gas, controlling the flow to be 200scc min < -1 >, stopping introducing ethylene gas after 90min, cooling the obtained product to room temperature along with the furnace, and obtaining a chemical vapor deposition product, wherein the volume mass ratio of the ethylene gas to the pretreated calcium silicide is 18L: 8 g.
adding the chemical vapor deposition product into hydrochloric acid with the mass fraction of 20%, stirring and reacting for 4h at room temperature, then filtering, washing for many times to be neutral, and drying the product to obtain the lithium ion battery negative electrode material, wherein the volume mass ratio of the hydrochloric acid to the chemical vapor deposition product is 200 mL: 12 g.
The obtained lithium ion battery negative electrode material is subjected to particle size D50 and specific surface area tests, and the test results are as follows: the median particle diameter D50 of the lithium ion battery negative electrode material is 4 μm, and the specific surface area is 5.4m 2/g.
The invention relates to a lithium ion battery cathode material, a binder (styrene butadiene rubber (SBR): sodium carboxymethyl cellulose (CMC): 3: 7 mass ratio) and a conductive agent Super P, wherein the weight ratio of the Styrene Butadiene Rubber (SBR): sodium carboxymethyl cellulose (CMC): 3: 7) to the conductive agent Super P is as follows that 80: 10: 10, adding a proper amount of water as a dispersing agent to prepare slurry, then uniformly coating the slurry on a copper foil current collector, and preparing a negative plate through vacuum drying and rolling; a simulated battery is assembled in a glove box under the protection of argon by using metal lithium as a counter electrode, 1mol/L mixed solvent of LiPF6 (EC: DMC is 1:1 volume ratio) as electrolyte and a polypropylene microporous membrane (Celgard 2400) as a diaphragm. And (3) carrying out constant-current charge and discharge test on the assembled analog battery on a Land tester (Wuhanxinnuo electronics Co., Ltd.), wherein the current density of charge and discharge is 150mA g-1, and the charge and discharge voltage interval is 0.001-1.5V.
Experiment results show that the first discharge specific capacity of the lithium ion battery provided by the invention is 1326mAh/g, and the first coulombic efficiency is 78.9%; after the charge and the discharge are cycled for 100 times, the capacity retention rate is 84.2%, the coulombic efficiency is 99.7%, and the cycle performance is better.
example 5
placing calcium silicide particles with the calcium content of 30% in a ball milling tank, adding absolute ethyl alcohol as a ball milling medium, and carrying out high-energy mechanical ball milling for 8 hours at the rotating speed of 400rpm under the protection of argon atmosphere to obtain the low-particle-size calcium silicide slurry.
adding the obtained low-particle-size calcium silicide slurry into 2mol/L sodium hydroxide aqueous solution, stirring and reacting for 20h at 25 ℃, then filtering and drying in vacuum to obtain pre-treated calcium silicide with the particle size of 3 mu m, wherein the mass ratio of sodium hydroxide to calcium silicide particles is 10: 4.
Placing pretreated calcium silicide in a quartz tube furnace, heating in the argon atmosphere, controlling the flow of argon to be 200scc min < -1 >, controlling the heating rate to be 10 ℃ min < -1 > after heating, stopping heating and preserving heat after heating to 900 ℃, introducing ethylene gas, controlling the flow to be 200scc min < -1 >, stopping introducing ethylene gas after 45min, cooling the obtained product to room temperature along with the furnace, and obtaining a chemical vapor deposition product, wherein the volume mass ratio of the ethylene gas to the pretreated calcium silicide is 24L: 8 g.
Adding the chemical vapor deposition product into hydrochloric acid with the mass fraction of 20%, stirring and reacting for 4h at room temperature, then filtering, washing for many times to be neutral, and drying the product to obtain the lithium ion battery negative electrode material, wherein the volume mass ratio of the hydrochloric acid to the chemical vapor deposition product is 250 mL: 10 g.
The obtained lithium ion battery negative electrode material is subjected to particle size D50 and specific surface area tests, and the test results are as follows: the median particle diameter D50 of the lithium ion battery negative electrode material is 4 μm, and the specific surface area is 5.4m 2/g.
The invention relates to a lithium ion battery cathode material, a binder (styrene butadiene rubber (SBR): sodium carboxymethyl cellulose (CMC): 3: 7 mass ratio) and a conductive agent Super P, wherein the weight ratio of the Styrene Butadiene Rubber (SBR): sodium carboxymethyl cellulose (CMC): 3: 7) to the conductive agent Super P is as follows that 80: 10: 10, adding a proper amount of water as a dispersing agent to prepare slurry, then uniformly coating the slurry on a copper foil current collector, and preparing a negative plate through vacuum drying and rolling; a simulated battery is assembled in a glove box under the protection of argon by using metal lithium as a counter electrode, 1mol/L mixed solvent of LiPF6 (EC: DMC is 1:1 volume ratio) as electrolyte and a polypropylene microporous membrane (Celgard 2400) as a diaphragm. And (3) carrying out constant-current charge and discharge test on the assembled analog battery on a Land tester (Wuhanxinnuo electronics Co., Ltd.), wherein the current density of charge and discharge is 150mA g-1, and the charge and discharge voltage interval is 0.001-1.5V.
the experimental result shows that the first discharge specific capacity of the lithium ion battery provided by the invention is 1633mAh/g, and the first coulombic efficiency is 81.8%; after the charge and the discharge are cycled for 100 times, the capacity retention rate is 92.6%, the coulombic efficiency is 99.9%, and the cycle performance is better.
Example 6
Placing calcium silicide particles with the calcium content of 30% in a ball milling tank, adding absolute ethyl alcohol as a ball milling medium, and mechanically milling for 6 hours at the rotating speed of 400rpm under the protection of argon atmosphere to obtain the low-particle-size calcium silicide slurry.
Adding the obtained low-particle-size calcium silicide slurry into 0.5mol/L sodium hydroxide aqueous solution, stirring and reacting for 10 hours at 35 ℃, then filtering and drying in vacuum to obtain pretreated calcium silicide with the particle size of 5 mu m, wherein the mass ratio of sodium hydroxide to calcium silicide particles is 8: 5.
placing pretreated calcium silicide in a quartz tube furnace, heating in the argon atmosphere, controlling the flow of argon to be 200scc min < -1 >, controlling the heating rate to be 7 ℃ min < -1 > after heating, stopping heating and preserving heat after heating to 900 ℃, introducing ethylene gas, controlling the flow to be 200scc min < -1 >, stopping introducing ethylene gas after 60min, cooling the obtained product to room temperature along with the furnace, and obtaining a chemical vapor deposition product, wherein the volume mass ratio of the ethylene gas to the pretreated calcium silicide is 36L: 4g of the total weight.
Adding the chemical vapor deposition product into hydrochloric acid with the mass fraction of 30%, stirring and reacting for 2h at room temperature, then filtering, washing for many times to be neutral, and drying the product to obtain the lithium ion battery negative electrode material, wherein the volume mass ratio of the hydrochloric acid to the chemical vapor deposition product is 200 mL: 10 g.
The obtained lithium ion battery negative electrode material is subjected to particle size D50 and specific surface area tests, and the test results are as follows: the median particle diameter D50 of the lithium ion battery negative electrode material is 8 μm, and the specific surface area is 3.2m 2/g.
The invention relates to a lithium ion battery cathode material, a binder (styrene butadiene rubber (SBR): sodium carboxymethyl cellulose (CMC): 3: 7 mass ratio) and a conductive agent Super P, wherein the weight ratio of the Styrene Butadiene Rubber (SBR): sodium carboxymethyl cellulose (CMC): 3: 7) to the conductive agent Super P is as follows that 80: 10: 10, adding a proper amount of water as a dispersing agent to prepare slurry, then uniformly coating the slurry on a copper foil current collector, and preparing a negative plate through vacuum drying and rolling; a simulated battery is assembled in a glove box under the protection of argon by using metal lithium as a counter electrode, 1mol/L mixed solvent of LiPF6 (EC: DMC is 1:1 volume ratio) as electrolyte and a polypropylene microporous membrane (Celgard 2400) as a diaphragm. The assembled analog battery is subjected to constant-current charge and discharge test on a Land tester (Wuhanxinnuo electronic Co., Ltd., please confirm the inventor), the current density of charge and discharge is 150mA g-1, and the charge and discharge voltage interval is 0.001-1.5V.
The experimental result shows that the first discharge specific capacity of the lithium ion battery provided by the invention is 1358mAh/g, and the first coulombic efficiency is 77.6%; after the charge and the discharge are cycled for 100 times, the capacity retention rate is 88.3%, the coulombic efficiency is 99.8%, and the cycle performance is better.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. The preparation method of the lithium ion battery negative electrode material is characterized by comprising the following steps of:
A) Performing alkali treatment on calcium silicide to obtain pretreated calcium silicide;
B) heating the pretreated calcium silicide, and introducing a gaseous hydrocarbon compound to carry out chemical vapor deposition to obtain a chemical vapor deposition product;
C) Performing acid washing treatment on the chemical vapor deposition product to obtain a lithium ion battery cathode material; the acid solution adopted in the acid cleaning treatment is one or more selected from hydrochloric acid, nitric acid, hydrobromic acid and hydroiodic acid;
The lithium ion battery negative electrode material comprises a core and a shell, wherein a hollow layer is arranged between the core and the shell;
the shell is made of a carbon material, and the inner core is made of a porous silicon material;
the inner pore wall surface of the inner core is not adhered with carbon material.
2. The method for preparing the negative electrode material of the lithium ion battery according to claim 1, wherein the particle size of the pretreated calcium silicide is 500nm to 10 μm.
3. The preparation method of the lithium ion battery anode material according to claim 1, wherein in the step B), the heating of the pretreated calcium silicide specifically comprises: and (3) placing the pretreated calcium silicide in a high-temperature tube furnace, and heating in the presence of protective gas.
4. The preparation method of the lithium ion battery anode material according to claim 1, wherein the temperature of the chemical vapor deposition is 600-1000 ℃; the time of the chemical vapor deposition is 10 min-120 min.
5. the preparation method of the lithium ion battery anode material according to claim 1, wherein the acid solution is 5 to 36 mass percent.
6. The method for preparing the negative electrode material of the lithium ion battery according to claim 1, wherein the thickness of the shell is 100nm to 5 μm.
7. The preparation method of the negative electrode material for the lithium ion battery, according to claim 1, wherein the particle size of the core is 500nm to 10 μm, and the pore size of the core is 10nm to 100 nm.
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