CN111342031A - 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
- Publication number
- CN111342031A CN111342031A CN202010232429.9A CN202010232429A CN111342031A CN 111342031 A CN111342031 A CN 111342031A CN 202010232429 A CN202010232429 A CN 202010232429A CN 111342031 A CN111342031 A CN 111342031A
- Authority
- CN
- China
- Prior art keywords
- negative electrode
- electrode material
- lithium
- salt
- efficiency
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a multi-gradient composite high-efficiency first-efficiency 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 conducting capacity 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, silicon monoxide, 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, irreversible products such as lithium oxide and lithium silicate can be generated by the silicon monoxide, so that 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. Mg-doped modified silicon oxide materials are also synthesized by homogeneous phase gas phase reaction, the first coulombic efficiency is improved to a certain extent, but Mg and silicon monoxide react quickly, so that the silicon monoxide is rapidly diverged into Si and SiO2The 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: 1-70: 1; in the buffer layer, the molar ratio of the lithium salt to the magnesium salt is 1: 1-0.5: 1.
Further, the lithium salt and the magnesium salt are calculated by taking the total mass of the negative electrode material as 100%, wherein the mass percentage of the lithium salt and the magnesium salt is 3-83%.
Further, the general formula of the silicon-oxygen compound is SiOxWherein, 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 2-1000 nm, preferably 5-200 nm.
Further, the chemical general formula of the lithium salt is LiaSibOcWherein a is>0, b is more than or equal to 0, and c is more than 0; the chemical general formula of the magnesium salt is MgASiBOCWherein A is>0, B is more than or equal to 0, and C is more than 0. Preferably, the lithium salt includes Li2SiO3、Li2Si2O5、Li4SiO4、Li6Si2O7One or more combinations of (a); the magnesium salt comprises MgSiO3、Mg2SiO4、Mg4SiO6One 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: 1-70: 1, preferably 20: 1-40: 1, and the lithium salt is excessive, so that a large amount of active oxygen can be consumed, and the first coulombic efficiency is greatly improved; if the molar ratio is less than 1:1, the lithium ion doping is insufficient, the first-effect coulombic efficiency is not obviously improved, and if the molar ratio is more than 70:1, the slurry stability and the material processability are poor. In the buffer layer, the molar ratio of lithium salt to magnesium salt is 1: 1-0.5: 1, 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 an inner core, and thus the structural damage or collapse of the silicon material due to volume expansion in the charge and discharge process is prevented; if the molar ratio is less than 0.5:1, excessive doping of magnesium ions will result in low material capacity, and if it is greater than 1:1, the material structure will be unstable and the buffer volume expansion effect will be poor. 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 3-83%, preferably 13-73% calculated by the total mass of the negative electrode material being 100%; 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 13-73%, and the best effect among first effect, circulation and capacity can be obtained.
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 carbon layer has a thickness of 2 to 1000nm, preferably 5 to 200 nm. 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 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.
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 addition amount and the reaction time of magnesium powder to concentrate more magnesium salts generated by reaction on the outer layer, so that the silica material precursor modified by magnesium doping and having 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-efficiency first-effect lithium battery composite material and the preparation method thereof provided by the invention 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 conducting capacity 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 volume expansion and improve cycle performance, the embodiment of the invention provides a multi-gradient composite high-first-efficiency lithium battery negative electrode material, as shown in fig. 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, lithium salt 4 and magnesium salt 5 which are present in the core 1 and the buffer layer 2, and the concentration of the magnesium salt 5 is gradually increased from the core 1 to the buffer layer 2, namely more magnesium salt 5 is present in the buffer layer 2. Wherein the silicon oxide compound has the general formula of SiOx（0<x<2）。
In addition, in the inner core 1, the molar ratio of the lithium salt 4 to the magnesium salt 5 is 1: 1-70: 1, preferably 20: 1-40: 1; in the buffer layer 2, the molar ratio of the lithium salt 4 to the magnesium salt 5 is 1: 1-0.5: 1. The mass percentage of the lithium salt 4 and the magnesium salt 5 is 3-83%, preferably 13-73%, based on 100% of the total mass of the negative electrode material.
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 200 nm.
Lithium salt 4 has the chemical formula of LiaSibOcWherein a is>0, b is not less than 0, c is more than 0, and Li can be specifically used2SiO3、Li2Si2O5、Li4SiO4、Li6Si2O7One or more combinations of (a); magnesium salt 5 has the chemical general formula of MgASiBOCWherein A is>0, B is more than or equal to 0, C is more than 0, and the material can be MgSiO3、Mg2SiO4、Mg4SiO6One 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) to obtain the content of metal elements, 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 metal 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 1 h. Magnesium powder reacts with SiO at high temperature, and the reaction diffuses from the outer layer to the inner layer of the SiO core. 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. And then crushing and screening to obtain particles with the particle size of 1-10 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 80 nm. Mixing the composite powder obtained above with Li3And 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 2 h. And Li3N is pyrolyzed at high temperature, and active lithium is inserted into the silicon monoxide to complete prelithiation, so as to obtain the required negative electrode active material particles. Wherein, in the inner core, the molar ratio of the lithium salt to the 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 °2SiO3A peak of (a); at positions 2 θ =23.86 ° and 24.6 °, outNow Li2Si2O5A peak of (a); at positions 2 θ =22.9 °, 35.7 °, 36.5 ° and 39.7 °, Mg appears2SiO4A peak of (a); at the position of 2 θ =31.1 °, MgSiO appears3The 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 Li3The N powder has different mass, and the molar ratio of the lithium salt to the magnesium salt and the content of the lithium salt and the magnesium salt are changed.
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 lithium salt to magnesium salt is 40:1, and the content of lithium salt and magnesium salt is 35%.
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 onto a copper foil with the thickness of 9 mu m, coating the copper foil by using an experimental coater, and drying the coated copper foil for 6 hours at the temperature of 85 ℃ under the vacuum (-0.1 MPa) condition to obtain the negative electrode slice. 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. A CR2032 button cell is assembled in a glove box, a metal lithium sheet is taken as a counter electrode, a polypropylene microporous membrane is taken as a diaphragm, and 1mol/L LiPF6 in EC: DEC =1:1Vol% with 5.0% FEC as electrolyte. 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.
The prepared negative electrode material powder is mixed with a graphite negative electrode (mass ratio is 20: 80) to obtain mixed negative electrode powder, the mixed negative electrode powder, SP, CNT, CMC (sodium carboxymethylcellulose) and SBR (styrene butadiene rubber) are mixed according to the mass ratio of 95.2: 0.85: 0.15: 1.2: 2.6, the mixed negative electrode powder, the SP, the CNT, the SBR (styrene butadiene rubber) are continuously stirred for 8 hours to paste by a magnetic stirring machine, the stirred slurry is poured on a copper foil with the thickness of 9 mu m, the copper foil is coated by an experimental coater and then dried for 6 hours under the condition of vacuum (-0.1 MPa) at 85 ℃ to obtain a negative electrode plate, the mixed slurry is poured on a positive electrode material with the thickness of 16 mu m, the SP, the CNT and the PVDF (polyvinylidene fluoride) according to the mass ratio of 90: 2: 1: 7, a proper amount of N-methyl pyrrolidone (N-methyl pyrrolidone) is added as a solvent, the slurry is continuously stirred for 8 hours to paste by the magnetic stirrer, the slurry is poured on a glove with the thickness of 16 mu m, the slurry is coated by the experimental coater and then dried under the condition of vacuum (-0.1 MPa) at 85 ℃ to obtain a constant current discharge capacity retention ratio of 0.8 hours, the anode plate is sequentially rolled on a DEC-roll, the anode plate is rolled under the constant current retention ratio of 0.8, the constant current of 0.1, the constant current of 0.8-0.1, the 12 cm, the constant current of a constant current meter, the constant current meter is measured under the constant current meter, the constant.
The test results are shown in table 1.
TABLE 1 lithium cell negative electrode Material withholding test results
As can be seen from Table 1, the battery assembled by the multi-element gradient composite lithium battery cathode material provided by the invention has excellent performance, high first coulombic efficiency and good cycle performance, the performance of the cathode material prepared by the doping mode of magnesium salt gradient distribution is superior to that of the cathode material prepared by the dispersion doping mode, and meanwhile, the material obtained by adjusting the doping ratio of lithium salt and magnesium salt is taken as the lithium battery cathode material, so that the comprehensive performance of the battery can reach the best level.
The above examples are only intended to illustrate the technical solution of the present invention, but 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 (9)
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.
2. The negative electrode material of a lithium secondary battery as claimed in claim 1, wherein the magnesium salt concentration increases from the core to the buffer layer.
3. The negative electrode material of the multi-element gradient composite high-first-efficiency lithium battery as claimed in claim 1, wherein in the core, the molar ratio of the lithium salt to the magnesium salt is 1: 1-70: 1; in the buffer layer, the molar ratio of the lithium salt to the magnesium salt is 1: 1-0.5: 1.
4. The negative electrode material of the multi-element gradient composite high-first-efficiency lithium battery of claim 1, wherein the lithium salt and the magnesium salt are contained in an amount of 3-83% by mass based on 100% by mass of the total negative electrode material.
5. 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 SiOxWherein, 0<x<2。
6. 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 2-1000 nm, preferably 5-200 nm.
7. 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 LiaSibOcWherein a is>0, b is more than or equal to 0, and c is more than 0; the chemical general formula of the magnesium salt is MgASiBOCWherein A is>0，B≥0，C＞0。
8. The first high-efficiency lithium battery negative electrode material of claim 7, wherein the lithium salt comprises Li2SiO3、Li2Si2O5、Li4SiO4、Li6Si2O7One or more combinations of (a); the magnesium salt comprises MgSiO3、Mg2SiO4、Mg4SiO6One or more combinations thereof.
9. A method for preparing the negative electrode material of the multi-element gradient composite high-first-efficiency lithium battery as claimed in any one of the claims 1 to 8, wherein the method 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 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010232429.9A CN111342031B (en) | 2020-03-28 | 2020-03-28 | Multi-element gradient composite high-first-efficiency lithium battery negative electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010232429.9A CN111342031B (en) | 2020-03-28 | 2020-03-28 | Multi-element gradient composite high-first-efficiency lithium battery negative electrode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111342031A true CN111342031A (en) | 2020-06-26 |
| CN111342031B CN111342031B (en) | 2022-11-29 |
Family
ID=71184714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010232429.9A Active CN111342031B (en) | 2020-03-28 | 2020-03-28 | Multi-element gradient composite high-first-efficiency lithium battery negative electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111342031B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112186145A (en) * | 2020-09-08 | 2021-01-05 | 合肥国轩高科动力能源有限公司 | Magnesium reduced carbon coated silica material and preparation method and application thereof |
| CN112271277A (en) * | 2020-09-27 | 2021-01-26 | 溧阳天目先导电池材料科技有限公司 | Cathode material containing metal element gradient doping and application thereof |
| CN112397693A (en) * | 2020-10-10 | 2021-02-23 | 惠州锂威新能源科技有限公司 | High-rate rapid charging negative electrode material and preparation method thereof, negative electrode plate and battery |
| CN115275209A (en) * | 2022-09-28 | 2022-11-01 | 四川启睿克科技有限公司 | High-first-efficiency silicon cathode with stable structure, preparation method and lithium ion battery |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090028986A (en) * | 2007-09-17 | 2009-03-20 | 삼성에스디아이 주식회사 | Negative active material for lithium secondary battery, and method of preparing same |
| US20140057176A1 (en) * | 2012-08-23 | 2014-02-27 | Samsung Sdi Co., Ltd. | Silicon-based negative active material, preparing method of preparing same and rechargeable lithium battery including same |
| CN103700819A (en) * | 2013-12-30 | 2014-04-02 | 合肥国轩高科动力能源股份公司 | Preparation method of silicon composite anode material provided with gradient change coating layer on surface |
| US20160351947A1 (en) * | 2014-02-07 | 2016-12-01 | Shin-Etsu Chemical Co., Ltd. | Negative electrode material for non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery and method of producing the same, and non-aqueous electrolyte secondary battery |
| US20170077496A1 (en) * | 2015-09-11 | 2017-03-16 | Fu Jen Catholic University | Metal gradient-doped cathode material for lithium batteries and its production method |
| CN108461723A (en) * | 2018-02-11 | 2018-08-28 | 安普瑞斯（南京）有限公司 | A kind of silicon based composite material and preparation method thereof for lithium ion battery |
| CN108630887A (en) * | 2017-03-20 | 2018-10-09 | 大洲电子材料株式会社 | Si composite oxide and preparation method thereof for lithium secondary battery cathode material |
| CN109599551A (en) * | 2018-12-28 | 2019-04-09 | 安普瑞斯（南京）有限公司 | A kind of doping type multi-layer core-shell silicon based composite material and preparation method thereof for lithium ion battery |
| CN109755500A (en) * | 2018-12-05 | 2019-05-14 | 华为技术有限公司 | A kind of silicon oxygen composite negative pole material and preparation method thereof |
| WO2019112325A1 (en) * | 2017-12-05 | 2019-06-13 | 대주전자재료 주식회사 | Negative electrode active material for non-aqueous electrolyte secondary battery and method for producing same |
| KR20190092311A (en) * | 2018-01-30 | 2019-08-07 | 주식회사 엘지화학 | Negative electrode active material, method for preparing the negative electrode active material, negative electrode comprising the negative electrode active material, and lithium secondarty battery comprising the negative electrode |
| CN110176601A (en) * | 2019-05-20 | 2019-08-27 | 合肥国轩高科动力能源有限公司 | A kind of carbon coating oxidation Asia silicium cathode material and its preparation method and application |
| JP2019169354A (en) * | 2018-03-23 | 2019-10-03 | 三洋電機株式会社 | Negative electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery |
| CN110416543A (en) * | 2019-08-07 | 2019-11-05 | 宁德新能源科技有限公司 | Negative electrode material and electrochemical appliance and electronic device comprising it |
| CN110828786A (en) * | 2019-10-09 | 2020-02-21 | 兰溪致德新能源材料有限公司 | Preparation method of long-cycle silicon oxide/carbon composite negative electrode material |
-
2020
- 2020-03-28 CN CN202010232429.9A patent/CN111342031B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090028986A (en) * | 2007-09-17 | 2009-03-20 | 삼성에스디아이 주식회사 | Negative active material for lithium secondary battery, and method of preparing same |
| US20140057176A1 (en) * | 2012-08-23 | 2014-02-27 | Samsung Sdi Co., Ltd. | Silicon-based negative active material, preparing method of preparing same and rechargeable lithium battery including same |
| CN103700819A (en) * | 2013-12-30 | 2014-04-02 | 合肥国轩高科动力能源股份公司 | Preparation method of silicon composite anode material provided with gradient change coating layer on surface |
| US20160351947A1 (en) * | 2014-02-07 | 2016-12-01 | Shin-Etsu Chemical Co., Ltd. | Negative electrode material for non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery and method of producing the same, and non-aqueous electrolyte secondary battery |
| US20170077496A1 (en) * | 2015-09-11 | 2017-03-16 | Fu Jen Catholic University | Metal gradient-doped cathode material for lithium batteries and its production method |
| CN108630887A (en) * | 2017-03-20 | 2018-10-09 | 大洲电子材料株式会社 | Si composite oxide and preparation method thereof for lithium secondary battery cathode material |
| WO2019112325A1 (en) * | 2017-12-05 | 2019-06-13 | 대주전자재료 주식회사 | Negative electrode active material for non-aqueous electrolyte secondary battery and method for producing same |
| WO2019151774A1 (en) * | 2018-01-30 | 2019-08-08 | 주식회사 엘지화학 | Anode active material, preparation method for anode active material, anode comprising anode active material, and secondary battery comprising anode |
| KR20190092311A (en) * | 2018-01-30 | 2019-08-07 | 주식회사 엘지화학 | Negative electrode active material, method for preparing the negative electrode active material, negative electrode comprising the negative electrode active material, and lithium secondarty battery comprising the negative electrode |
| CN108461723A (en) * | 2018-02-11 | 2018-08-28 | 安普瑞斯（南京）有限公司 | A kind of silicon based composite material and preparation method thereof for lithium ion battery |
| JP2019169354A (en) * | 2018-03-23 | 2019-10-03 | 三洋電機株式会社 | Negative electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery |
| CN109755500A (en) * | 2018-12-05 | 2019-05-14 | 华为技术有限公司 | A kind of silicon oxygen composite negative pole material and preparation method thereof |
| CN109599551A (en) * | 2018-12-28 | 2019-04-09 | 安普瑞斯（南京）有限公司 | A kind of doping type multi-layer core-shell silicon based composite material and preparation method thereof for lithium ion battery |
| CN110176601A (en) * | 2019-05-20 | 2019-08-27 | 合肥国轩高科动力能源有限公司 | A kind of carbon coating oxidation Asia silicium cathode material and its preparation method and application |
| CN110416543A (en) * | 2019-08-07 | 2019-11-05 | 宁德新能源科技有限公司 | Negative electrode material and electrochemical appliance and electronic device comprising it |
| CN110828786A (en) * | 2019-10-09 | 2020-02-21 | 兰溪致德新能源材料有限公司 | Preparation method of long-cycle silicon oxide/carbon composite negative electrode material |
Non-Patent Citations (1)
| Title |
|---|
| PENG LI,ET AL.: ""Nano/Microstructured Silicon–Graphite Composite Anode for High-Energy-Density Li-Ion Battery"", 《ACS NANO》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112186145A (en) * | 2020-09-08 | 2021-01-05 | 合肥国轩高科动力能源有限公司 | Magnesium reduced carbon coated silica material and preparation method and application thereof |
| CN112271277A (en) * | 2020-09-27 | 2021-01-26 | 溧阳天目先导电池材料科技有限公司 | Cathode material containing metal element gradient doping and application thereof |
| WO2022062320A1 (en) * | 2020-09-27 | 2022-03-31 | 溧阳天目先导电池材料科技有限公司 | Negative electrode material on which metal element is gradient-doped and application thereof |
| 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 |
| CN112397693A (en) * | 2020-10-10 | 2021-02-23 | 惠州锂威新能源科技有限公司 | High-rate rapid charging negative electrode material and preparation method thereof, negative electrode plate and battery |
| CN115275209A (en) * | 2022-09-28 | 2022-11-01 | 四川启睿克科技有限公司 | High-first-efficiency silicon cathode with stable structure, preparation method and lithium ion battery |
| CN115275209B (en) * | 2022-09-28 | 2023-03-10 | 四川启睿克科技有限公司 | High-first-efficiency silicon cathode with stable structure, preparation method and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111342031B (en) | 2022-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112018367B (en) | Negative electrode active material for battery, preparation method of negative electrode active material, battery negative electrode and battery | |
| CN109273680B (en) | Porous silicon-carbon negative electrode material, preparation method thereof and lithium ion battery | |
| CN111342030B (en) | Multi-element composite high-first-efficiency lithium battery negative electrode material and preparation method thereof | |
| JP5826405B2 (en) | Nanosilicon carbon composite material and method for preparing the same | |
| JP7288059B2 (en) | Silicon-oxygen composite negative electrode material, its preparation method and lithium ion battery | |
| CN111342031B (en) | Multi-element gradient composite high-first-efficiency lithium battery negative electrode material and preparation method thereof | |
| CN113272991A (en) | Silicon-carbon composite anode material | |
| WO2022199389A1 (en) | Silicon-oxygen composite negative electrode material, preparation method therefor, and lithium ion battery | |
| CN112201779B (en) | Preparation method and application of silicon-based composite material slurry | |
| WO2022021933A1 (en) | Negative electrode material for nonaqueous electrolyte secondary battery, and preparation method therefor | |
| EP4156331A1 (en) | Silicon-carbon composite material for secondary lithium battery and preparation method therefor | |
| CN111463419B (en) | Silicon-based @ titanium niobium oxide core-shell structure anode material and preparation method thereof | |
| CN108682833B (en) | Preparation method of lithium iron phosphate-based modified cathode material | |
| CN113764642A (en) | Lithium-silicon oxide-containing composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN110880589B (en) | Carbon nanotube @ titanium dioxide nanocrystal @ carbon composite material and preparation method and application thereof | |
| CN112661163B (en) | Silica-based composite anode material, preparation method thereof and lithium ion battery | |
| CN111009647A (en) | Lithium borosilicate alloy cathode active material of lithium secondary battery, cathode, preparation and application thereof | |
| CN111463423A (en) | Preparation method of negative electrode material of silicon oxide lithium ion battery and preparation method of negative electrode piece of battery | |
| CN112928246B (en) | Composite material, preparation method and application thereof | |
| CN113871574B (en) | Lithium ion battery negative plate and preparation method and application thereof | |
| CN116477661A (en) | Lithium supplementing material and preparation method and application thereof | |
| CN108987689B (en) | Preparation method of silicon-carbon negative electrode material | |
| Noerochim et al. | High electrochemical performance of Li 4 Ti 5 O 12/C synthesized by ball milling and direct flaming of acetylene gas as anode for lithium-ion battery | |
| CN116190660B (en) | Adhesive, preparation method and application thereof, silicon-based negative electrode and preparation method thereof | |
| CN117133907B (en) | Carbon-coated silicon composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |