CN111342031B - Multi-element gradient composite high-first-efficiency lithium battery negative electrode material and preparation method thereof - Google Patents
Multi-element gradient composite high-first-efficiency lithium battery negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a multi-gradient composite high-efficiency first-effect lithium battery cathode material and a preparation method thereof, wherein the cathode material is of a multilayer core-shell structure and comprises an inner core, a buffer layer and an outer layer; the inner core and the buffer layer of the negative electrode material are silicon-oxygen compounds, and the outer layer is a carbon coating layer; the inner core and the buffer layer also contain lithium salt and magnesium salt, and the concentration of the magnesium salt is gradually increased from the inner core to the buffer layer to form gradient distribution. Lithium salts in the cathode material core body are excessive, so that a large amount of active oxygen can be consumed, the initial coulombic efficiency of the material is effectively improved, and the ion conductivity of the material is improved; and the buffer layer contains a large amount of magnesium silicate, so that the first charge-discharge efficiency of the material is further improved, and meanwhile, the magnesium silicate forms a high-strength protective layer, so that the structural stability of the material is enhanced, and the cycle performance of the material is improved.
Description
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a multi-element gradient composite high-efficiency first-effect lithium battery negative electrode material and a preparation method thereof.
Background
The silicon material has piezoelectric characteristics similar to those of graphite and high lithium storage specific capacity, and is widely researched. Currently, the main forms of research and application of silicon-based materials include pure Si, silica, silicon carbon, and silicon alloys. In contrast, silica and silicon carbon are more mature and more widely used. However, in the process of first lithium intercalation, silicon monoxide can generate irreversible products such as lithium oxide and lithium silicate, and the first coulombic efficiency is low.
In order to solve the problems, researchers carry out pre-lithiation modification treatment on a silicon oxide material by a thermal doping method, so that the first coulombic efficiency is greatly improved, but the lithium doping modification condition is harsh, the production cost is high, and the slurry after lithium doping is unstable. The first coulombic efficiency is improved to a certain extent by synthesizing Mg-doped modified silicon oxide material through homogeneous phase gas phase reaction, but Mg and silicon monoxide react quickly to cause the silicon monoxide to be diverged into Si and SiO rapidly 2 The Si crystal grows rapidly, resulting in a reduced cycle life, and the first coulombic efficiency does not meet the use requirements.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a multi-element gradient composite high-efficiency lithium battery cathode material and a preparation method thereof. The purpose of the invention is realized by the following technical scheme:
the invention provides a multi-gradient composite high-first-efficiency lithium battery cathode material, which comprises a multi-layer core-shell structure consisting of a silicon oxide compound core, a buffer layer and a carbon coating layer which are sequentially distributed from inside to outside, wherein the core and the buffer layer of the cathode material also comprise lithium salt and magnesium salt, and the concentration of the magnesium salt is gradually increased from the core to the buffer layer.
Further, in the inner core, the molar ratio of the lithium salt to the magnesium salt is 1 to 1; in the buffer layer, the molar ratio of the lithium salt to the magnesium salt is 1 to 0.5.
Further, the mass percentage of the lithium salt and the magnesium salt is 3-83% based on the total mass of the negative electrode material as 100%.
Further, the general formula of the silicon-oxygen compound is SiO x Wherein, 0<x<2。
Further, the carbon of the carbon coating layer comprises one or more of soft carbon, hard carbon, carbon black, graphite, graphene, carbon nanotubes, carbon fibers and mesocarbon microbeads; the thickness of the carbon coating layer is 2 to 1000nm, and preferably 5 to 200nm.
Further, it is characterized byThe chemical general formula of the lithium salt is Li a Si b O c Wherein a is>0, b is more than or equal to 0, c is more than 0; the chemical general formula of the magnesium salt is Mg A Si B O C Wherein A is>0, B is more than or equal to 0, and C is more than 0. Preferably, the lithium salt includes Li 2 SiO 3 、Li 2 Si 2 O 5 、Li 4 SiO 4 、Li 6 Si 2 O 7 One or more combinations of (a); the magnesium salt comprises MgSiO 3 、Mg 2 SiO 4 、Mg 4 SiO 6 One or more combinations thereof.
The core and the buffer layer of the cathode material comprise lithium salt and magnesium salt, and the concentration of the magnesium salt is gradually increased from the core to the buffer layer to form gradient distribution. In the inner core, the molar ratio of the lithium salt to the magnesium salt is 1 to 70, preferably 20; if the molar ratio is less than 1. In the buffer layer, the molar ratio of the lithium salt to the magnesium salt is 1 to 0.5, the magnesium salt is excessive and mainly forms magnesium silicate, so that the buffer layer has good structural strength and can generate a protective layer on the surface of the inner core, thereby preventing the structural damage or collapse of the silicon material caused by volume expansion in the charging and discharging processes; if the molar ratio is less than 0.5, excessive doping of magnesium ions will result in a low material capacity, and if the molar ratio is greater than 1. Therefore, the molar ratio of the lithium salt to the magnesium salt is controlled within a certain range, the best effect can be achieved, and the problems of low first effect, poor circulation and the like of the material can be caused by excess or deficiency.
The mass percentage of the lithium salt and the magnesium salt is 3 to 83 percent, preferably 13 to 73 percent, calculated by taking the total mass of the negative electrode material as 100 percent; less than 3% results in poor volume expansion effect of the buffer material, low coulombic effect for the first time and poor circulation stability, and more than 83% results in obvious capacity reduction, poor slurry stability and poor material processability. Preferably 13 to 73 percent, and the best effect can be obtained among the first effect, the circulation and the capacity.
The carbon in the carbon layer comprises one or more of soft carbon, hard carbon, carbon black, graphite, graphene, carbon nanotubes, carbon fibers and mesocarbon microbeads; the thickness of the carbon layer is 2 to 1000nm, and preferably 5 to 200nm. If the thickness of the carbon layer is too small, the buffer volume expansion effect is not obvious, the conductivity is not greatly improved, and the cycle performance is poor; too large a carbon layer thickness indicates that too high a carbon content will decrease the anode capacity and make the bulk density too low, thereby decreasing the charge and discharge capacity per unit volume.
The invention also aims to provide a preparation method of the multi-element gradient composite high-first-efficiency lithium battery anode material, which comprises the following steps:
(1) A modification procedure: mixing silicon oxide powder with magnesium powder, and sintering;
(2) A coating procedure: coating the sintered product with a conductive layer;
(3) A pre-lithiation step: lithium is inserted into the coated material to form a lithium salt in the silicon oxide compound, thereby obtaining a multi-component doped negative electrode active material particle.
According to the preparation method of the multi-gradient composite high-first-efficiency lithium battery cathode material, provided by the invention, the modification procedure is to mix silica compound powder with magnesium powder and sinter the mixture at a certain temperature to obtain the magnesium-doped modified silica compound material. The process is a solid-solid reaction, and magnesium starts to react from the outer shell of the silicon-oxygen compound and gradually permeates into the inner core. Technicians can control the adding amount of magnesium powder and the reaction time to concentrate more magnesium salts generated by the reaction on the outer layer, so that the silica material precursor which is modified by doping magnesium and has a gradient structure is obtained.
The coating process is to coat the surface of the silicon monoxide precursor with conductive carbon by one or more of liquid phase coating, solid phase coating, vapor deposition coating or mechanical coating.
The pre-lithiation process is to dope a lithium compound by one or more of a gas phase CVD method, a thermal doping method, a redox method, or an electrochemical method.
Compared with the prior art, the multi-element gradient composite high-first-efficiency lithium battery composite material and the preparation method thereof have the following beneficial effects:
(1) In the aspect of material structure, lithium salt in a silicon-oxygen compound nucleus body is more, so that a large amount of active oxygen can be consumed, the first coulombic efficiency of the material is improved, and the ion conductivity of the material is improved; the magnesium silicate on the surface of the silicon-oxygen compound is more, so that the first charge-discharge efficiency of the material is further improved, and meanwhile, the magnesium silicate forms a high-strength protective layer, so that the structural stability of the material is enhanced, and the cycle performance of the material is improved; in addition, the multi-element gradient composite system realizes good interface combination.
(2) In the aspect of preparation process, the lithium-doped modification condition is harsh, the cost is high, the slurry is unstable, but the first effect is good; the magnesium-doped modification condition is simple, the cost is low, the slurry is stable, but the first effect is common. The two are modified in a matching way, so that the operation risk can be reduced, the cost can be reduced, and the modification effect can be improved.
Drawings
FIG. 1 is a schematic structural diagram of a multi-element gradient composite high-efficiency first-efficiency lithium battery composite material according to an embodiment of the present invention;
figure 2 XRD pattern of inventive example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but 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.
In order to greatly improve the first coulombic efficiency of the silicon-based negative electrode material and simultaneously relieve the volume expansion and improve the cycle performance, the embodiment of the invention provides a multi-gradient composite high-efficiency first-effect lithium battery negative electrode material, as shown in figure 1, the negative electrode material is of a multi-layer core-shell structure and comprises a silica compound core 1, a buffer layer 2, a carbon coating layer 3 and a carbon oxide layer existing in the core 11 and lithium salt 4 and magnesium salt 5 in buffer layer 2, and the concentration of magnesium salt 5 increases from core 1 to buffer layer 2, i.e. magnesium salt 5 is more present in buffer layer 2. Wherein the silicon oxide compound has the general formula of SiO x （0<x<2）。
Furthermore, in the inner core 1, the molar ratio of the lithium salt 4 to the magnesium salt 5 is 1; in the buffer layer 2, the molar ratio of the lithium salt 4 to the magnesium salt 5 is 1 to 0.5. The mass percentage of the lithium salt 4 and the magnesium salt 5 is 3 to 83 percent, preferably 13 to 73 percent, based on the total mass of the negative electrode material as 100 percent.
The carbon of the carbon coating layer 3 comprises one or more of soft carbon, hard carbon, carbon black, graphite, graphene, carbon nanotubes, carbon fibers and mesocarbon microbeads; the thickness of the carbon coating layer 3 is 2 to 1000nm, preferably 5 to 200nm.
Lithium salt 4 has the chemical formula of Li a Si b O c Wherein a is>0, b is not less than 0, c is more than 0, and specifically Li 2 SiO 3 、Li 2 Si 2 O 5 、Li 4 SiO 4 、Li 6 Si 2 O 7 One or more combinations of (a); magnesium salt 5 has the chemical general formula of Mg A Si B O C Wherein A is>0, B is more than or equal to 0, C is more than 0, and the material can be MgSiO 3 、Mg 2 SiO 4 、Mg 4 SiO 6 One or more combinations thereof.
The embodiment of the invention correspondingly provides a preparation method of the material, and in order to better understand the preparation process and the performance characteristics of the material provided by the invention, the following description is combined with specific embodiments. The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
In the embodiment, the content of lithium salt and magnesium salt in the multi-element gradient composite negative electrode material is measured by inductively coupled plasma atomic emission spectrometry (ICP-OES), and then the content and the molar ratio of corresponding compounds are calculated.
Example 1
SiO powder with the medium diameter D50=5 μm and magnesium powder are uniformly mixed and then are added into a high-temperature furnace for heat treatment. Heating to 1100 deg.C under argon protection, and heat treating for 1h. Magnesium powder reacts with SiO at high temperature, and the reaction diffuses from the outer layer of the SiO core to the inner layer. By controlling the using amount of magnesium powder and the heat treatment time, more reaction occurs on the outer layer of the SiO core, so that the magnesium-doped modified silicon monoxide precursor with the core-shell structure is obtained. Then crushing and screening to obtain particles with the particle size of 1 to 10 mu m.
The particles obtained above were charged into a CVD furnace, and propylene at a flow rate of 9L/min and argon at a flow rate of 18L/min were introduced for a deposition time of 1 hour. Cracking propylene at high temperature, coating pyrolytic carbon on the particle surface to obtain carbon-coated magnesium-doped SiO composite powder, wherein the thickness of the carbon coating layer is 80nm. Mixing the composite powder obtained above with Li 3 And uniformly mixing the N powder, and simultaneously adding the N powder into a high-temperature furnace for heat treatment. Heating to 800 ℃ under the protection of argon, and the heat treatment time is 2h. And pyrolyzing Li3N at high temperature, and inserting active lithium into the silicon monoxide to complete prelithiation to obtain the required negative electrode active material particles. Wherein, in the inner core, the molar ratio of lithium salt to magnesium salt is 35:1; in the buffer layer, the molar ratio of lithium salt to magnesium salt is 0.75:1. the content of lithium and magnesium salts was 36%.
An X-ray diffraction analyzer (TD-3500 model, dandongtongda instruments ltd.) was used to analyze the X-ray diffraction peaks of the multi-element gradient composite anode material, and fig. 2 is the XRD diffraction pattern of the multi-element gradient composite anode material prepared in example 1, and it can be seen that Li appears at the positions of 2 θ =18.9 °, 27 °, 33.1 °, 38.6 ° and 43.4 ° 2 SiO 3 A peak of (a); at positions of 2 θ =23.86 ° and 24.6 °, li appears 2 Si 2 O 5 A peak of (a); at positions 2 θ =22.9 °, 35.7 °, 36.5 ° and 39.7 °, mg appears 2 SiO 4 A peak of (a); at the position of 2 θ =31.1 °, mgSiO appears 3 The peak of (a) indicates that Li and Mg are successfully doped in the form of silicate.
Examples 2 to 5
The other steps and process parameters were the same as in example 1, except that the amount of added magnesium metal powder and Li 3 The quality of N powder is different, the lithium salt andthe molar ratio of magnesium salts, and the content of lithium and magnesium salts.
Comparative example 1
And uniformly mixing silicon powder, silicon dioxide powder and magnesium powder, heating for sublimation, and cooling to obtain the magnesium uniformly-doped modified silicon monoxide precursor. And carrying out carbon coating and pre-lithiation treatment on the silicon monoxide precursor to prepare the lithium and magnesium gradient-free co-doped silicon-carbon negative electrode material. The molar ratio of the lithium salt to the magnesium salt is 40.
The lithium battery negative electrode materials prepared in the examples and the comparative examples were assembled into lithium batteries, respectively, and the chemical properties thereof were tested.
First, the first efficiency of the material is obtained in the following manner. According to the mass ratio of 80:9:1:10 mixing the prepared anode material powder: SP (carbon black): CNT (carbon nanotube): PAA (polyacrylic acid) is mixed, a proper amount of deionized water is added as a solvent, and the mixture is continuously stirred for 8 hours to be pasty by a magnetic stirrer. And pouring the stirred slurry on a copper foil with the thickness of 9 mu m, coating the copper foil by using an experimental coater, and drying the copper foil for 6 hours at the temperature of 85 ℃ under the vacuum (-0.1 MPa) condition to obtain the negative electrode piece. Rolling the electrode sheet to 100 μm on a manual double-roller machine, making into 12mm diameter wafer with a sheet punching machine, drying at 85 deg.C under vacuum (-0.1 MPa) for 8 hr, weighing, and calculating active substance weight. CR2032 type button cell was assembled in a glove box, using a metal lithium sheet as a counter electrode, a polypropylene microporous membrane as a separator, 1mol/L LiPF6 in EC: DEC =1 Vol% with 5.0% fec as an electrolyte solution. And standing the prepared button cell for 12h at room temperature, performing constant-current charge-discharge test on a blue-ray test system, performing charge-discharge at a current of 0.1C, and obtaining the first efficiency of the cathode material at a delithiation cut-off voltage of 1.5V.
Further, the capacity retention rate was calculated in the following manner. Mixing the prepared negative electrode material powder with a graphite negative electrode (mass ratio 20: 0.85:0.15:1.2:2.6 mixing the mixed negative electrode powder, SP, CNT, CMC (sodium carboxymethylcellulose) and SBR (styrene butadiene rubber), and continuously stirring for 8h to be pasty by using a magnetic stirrer. And pouring the stirred slurry onto a copper foil with the thickness of 9 mu m, coating by using an experimental coater, and drying for 6 hours at the temperature of 85 ℃ under the vacuum (-0.1 MPa) condition to obtain the negative electrode plate. Then, according to the mass ratio of 90:2:1:7 mixing 811 positive electrode material, SP, CNT and PVDF (polyvinylidene fluoride), adding a proper amount of NMP (N-methyl pyrrolidone) as a solvent, and continuously stirring for 8h to be pasty by a magnetic stirrer. Pouring the stirred slurry on an aluminum foil with the thickness of 16 mu m, coating the aluminum foil by using an experimental coater, and drying the aluminum foil for 6 hours at the temperature of 85 ℃ under the vacuum (-0.1 MPa) condition to obtain the positive electrode piece. Rolling the positive and negative electrode plates to 100 μm on a manual double-roller machine, making into 12mm diameter wafer with a sheet punching machine, drying at 85 deg.C under vacuum (-0.1 MPa) for 8h, weighing, and calculating active substance weight. A CR2032 type button full cell was assembled in a glove box, 1mol/L LiPF6 in EC: DEC = 1. And standing the prepared button full cell for 12 hours at room temperature, performing constant-current charge and discharge test on a blue test system, and performing charge and discharge at a current of 0.25 ℃ with a charge and discharge cutoff voltage of 3.0-4.25V. The capacity retention rate was calculated from the discharge capacity at the 100 th cycle/the discharge capacity at the 1 st cycle × 100%.
The test results are shown in table 1.
TABLE 1 lithium battery negative electrode Material withholding test results
As can be seen from Table 1, the battery assembled by the multi-element gradient composite lithium battery negative electrode material provided by the invention has excellent performance, high initial coulombic efficiency and good cycle performance, the performance of the negative electrode material prepared by the doping mode of magnesium salt gradient distribution is superior to that of the negative electrode material prepared by the dispersion doping mode, and meanwhile, the material obtained by adjusting the doping ratio of lithium salt and magnesium salt is used as the lithium battery negative electrode material, so that the comprehensive performance of the battery can reach the optimal level.
The above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. The multi-element gradient composite high-first-efficiency lithium battery cathode material is characterized in that the cathode material is of a multilayer core-shell structure and comprises an inner core, a buffer layer and an outer layer;
the inner core and the buffer layer of the negative electrode material are silicon-oxygen compounds, and the outer layer is a carbon coating layer;
the inner core and the buffer layer also contain lithium salt and magnesium salt;
in the inner core, the molar ratio of the lithium salt to the magnesium salt is 20 to 1; in the buffer layer, the molar ratio of the lithium salt to the magnesium salt is 1 to 0.5; the magnesium salt concentration increases from the inner core to the buffer layer;
the preparation method of the multi-element gradient composite high-first-efficiency lithium battery negative electrode material comprises the following steps of:
(1) A modification procedure: mixing silicon oxide powder with magnesium powder, and sintering;
(2) A coating procedure: coating the sintered product with a conductive layer;
(3) A pre-lithiation process: lithium is inserted into the coated material to form a lithium salt in the silicon oxide compound, thereby obtaining a multi-component doped negative electrode active material particle.
2. The negative electrode material of the multi-element gradient composite high-first-efficiency lithium battery as claimed in claim 1, wherein the lithium salt and the magnesium salt are contained in an amount of 3 to 83% by mass, based on 100% by mass of the total negative electrode material.
3. The multi-element gradient composite high-first-efficiency lithium battery negative electrode material as claimed in claim 1, wherein the general formula of the silica compound is SiO x Wherein, 0<x<2。
4. The multi-element gradient composite high-first-efficiency lithium battery negative electrode material as claimed in claim 1, wherein the carbon of the carbon coating layer comprises one or more of soft carbon, hard carbon, carbon black, graphite, graphene, carbon nanotubes, carbon fibers, mesocarbon microbeads; the thickness of the carbon coating layer is 2 to 1000nm.
5. The cathode material for the multi-element gradient composite high-first-efficiency lithium battery as claimed in claim 4, wherein the thickness of the carbon coating is 5 to 200nm.
6. The multi-element gradient composite high-first-efficiency lithium battery negative electrode material as claimed in claim 1, wherein the chemical general formula of the lithium salt is Li a Si b O c Wherein a is>0, b is more than or equal to 0, c is more than 0; the chemical general formula of the magnesium salt is Mg A Si B O C Wherein A is>0，B≥0，C＞0。
7. The first high-efficiency lithium battery negative electrode material of claim 6, wherein the lithium salt comprises Li 2 SiO 3 、Li 2 Si 2 O 5 、Li 4 SiO 4 、Li 6 Si 2 O 7 One or more combinations of (a); the magnesium salt comprises MgSiO 3 、Mg 2 SiO 4 、Mg 4 SiO 6 One or more combinations thereof.
8. A method for preparing the negative electrode material of the multi-gradient composite high-first-efficiency lithium battery as claimed in any one of the preceding claims 1 to 7, wherein the method comprises:
(1) A modification procedure: mixing silicon oxide powder with magnesium powder, and sintering;
(2) A coating procedure: coating the sintered product with a conductive layer;
(3) A pre-lithiation step: lithium is inserted into the coated material to form a lithium salt in the silicon oxide compound, thereby obtaining a multi-component doped negative electrode active material particle.
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| CN112271277B (en) * | 2020-09-27 | 2023-07-18 | 溧阳天目先导电池材料科技有限公司 | Negative electrode material containing metal element gradient doping and application thereof |
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