CN112194138A - Layered SiOx material and preparation method and application thereof - Google Patents
Layered SiOx material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a layered SiOx material which is an accordion-shaped layered micron-sized particle, wherein the particle size of the SiOx material is 0.5-20 mu m, slit gaps with nano-scale width exist between any two adjacent layers, the width of each slit gap is 1-50 nm, and the thickness of a single sheet layer is 30-40 nm; the preparation method comprises the following steps: dissolving CaSi2Ca in the solution is used for obtaining a laminated siloxene material; and (3) calcining at high temperature to remove hydrogen bonds, hydroxyl groups and the like on the surface of the siloxene to obtain the SiOx material. The preparation method has the advantages of simple preparation process, less flow, low requirement on equipment and easy industrialized mass production, and the obtained 2D layered SiOx material can be directly used as a lithium ion battery cathode material without being coated, thereby representing excellent electrochemical performance.
Description
Technical Field
The invention relates to the technical field of energy materials, in particular to a layered SiOx material and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high energy density, high working voltage, good cycle performance, low self-discharge rate, small environmental hazard and the like, occupies a leading position in the field of mobile electronic terminal equipment, and is also an ideal power supply system for electric vehicles and large-scale energy storage. With the rapid development of portable electronic devices and electric vehicles, the demand and performance requirements for lithium ion batteries have increased dramatically, and lithium ion batteries are urgently needed to develop toward higher energy density. The negative electrode material is an important factor influencing the energy density of the lithium ion battery. Graphite-based negative electrode material (theoretical capacity of 372mAh g only-1) Is the main cathode material used by the current commercial lithium ion battery, and can not meet the requirement of the high specific energy lithium ion battery. Therefore, finding a negative electrode material with ultrahigh lithium storage capacity to replace graphite materials is a research hotspot in the field of lithium ion batteries. Among non-carbon anode materials, silicon is one of the most promising next-generation lithium ion battery anode materials due to its ultra-high capacity advantage and appropriate lithium removal/insertion potential.
The silicon has extremely high theoretical specific capacity and lower lithium extraction potential (lower than 0.5V vs Li/Li)+) The lithium storage battery has the advantages of rich reserves, low cost and the like, but the volume expansion and shrinkage of the lithium storage battery is serious in the lithium extraction process, about 400 percent, so that a series of problems of material pulverization, unstable SEI film, serious capacity attenuation and the like are caused. The oxide of silicon generates an electrochemically inert component (Li) during the first discharge2O、LixSiyO) which buffer the volume expansion of silicon and thus help to obtain a specific ratio of materialSimple substance silicon has more stable cycle life, and silicon oxide has higher tap density than nano silicon, so the simple substance silicon has great potential in industrial application, but the patent literature has no report about 2D layer structured silicon oxide.
Therefore, how to provide a 2D layered SiOx material and a method for preparing the same are problems that need to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a preparation method of a layered SiOx material, namely, a method for preparing a CaSi material2And slowly etching and dissolving the Ca layer to obtain a layered siloxene material, and calcining the layered siloxene material in an inert atmosphere to obtain the layered SiOx material. The prepared laminated SiOx material can be used as a negative electrode material of a lithium ion battery and can show excellent electrochemical performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
the laminated SiOx material is in the form of accordion-shaped laminated micron-sized particles, the particle size of the SiOx material is 0.5-20 mu m, slit gaps with nanoscale width exist between any two adjacent layers, the width of each slit gap is 1-50 nm, and the thickness of each single sheet layer is 30-40 nm.
Preferably, in the above-mentioned one kind of layered SiOx material, a value of x in the SiOx material ranges from 0< x < 2.
The preparation method of the layered SiOx material comprises the following steps:
(1) preparing a solution: and respectively dissolving the substance A and the substance B in deionized water to obtain a solution A and a solution B.
(2) Preparing a laminated siloxene material: mixing the solution A with CaSi2Sequentially adding the materials into a reaction container, stirring the materials until the materials are uniformly mixed, adding the solution B, stirring the materials for reaction for 1 to 4 days, carrying out ultrasonic oscillation for 0.5 to 5 hours, washing the materials for 3 to 10 times by using deionized water, and drying the materials to obtain a layered siloxene material;
(3) preparing a layered SiOx material: and sintering the layered siloxene material for 0.5-5h in an inert atmosphere to obtain the layered SiOx material.
Hair brushMinghei CaSi2Is a precursor, has a structure that Ca layers and Si layers are alternately distributed, and is a good raw material for preparing the laminated silicon material.
Preferably, in the above method for preparing a layered SiOx material, in step (1), the substance a is a chlorine-containing inorganic salt including NaCl and AlCl3、MgCl2、KCl、LiCl、ZnCl2、CaCl2、CuCl2、FeCl3、CoCl2、NiCl2One or a mixture of a plurality of the components according to any proportion;
the substance B is HOOCCOOH, H2CO3、H2SO4、HNO3、H3PO4、HClO4、CH3COOH、CH3CH(OH)COOH、C6H8O7HCOOH and CH3CH2One or a mixture of more than one of COOH according to any proportion.
Preferably, in the above method for preparing a layered SiOx material, the concentration of the solution a in the step (1) is 0.1 to 15mol/L, and the concentration of the solution B is 0.1 to 12 mol/L.
Preferably, in the above method for preparing a layered SiOx material, the CaSi in step (2)2And solution a in a ratio of 1 g: (50-500) mL, wherein the volume ratio of the solution A to the solution B is 1: (0.5-2).
The beneficial effects of the above technical scheme are: is favorable to CaSi2The middle Ca layer is fully dissolved, so that a pure-phase siloxene material is obtained.
Preferably, in the preparation method of the layered SiOx material, the stirring speed in the step (2) is 200 to 1000 r/min; the adding rate of the solution B is V/2000-V/300 per minute, wherein V is the total volume of the solution B.
The beneficial effects of the above technical scheme are: the concentration of HCl in the reaction system can be controlled by controlling the adding speed of the solution B, wherein the HCl plays an etching role, the solution A provides Cl-, and the solution B provides H+Therefore, the adding speed of the solution B can control the amount of HCl in the system), thereby ensuring that the etching and dissolving process of Ca can be slowly and mildly carried outThereby obtaining the siloxene material with a laminated structure.
Preferably, in the preparation method of the layered SiOx material, the drying in the step (2) is vacuum drying or freeze drying, the vacuum drying temperature is 80 to 120 ℃, the freeze drying temperature is-35 to-50 ℃, and the drying time is 10 to 24 hours.
The beneficial effects of the above technical scheme are: the drying process prevents further oxidation of the SiOx material upon drying.
And in the step (2), the ultrasonic oscillation can increase the interlayer distance of siloxene to generate more interlayer gaps, the interlayer gaps are favorable for accommodating the volume change of the silicon material in the lithium desorption process, the setting of ultrasonic parameters can ensure that the interlayer bonding force can be damaged in the ultrasonic process, the interlayer gaps are increased, and the volume change of the silicon material in the lithium desorption process is favorable for accommodating.
Preferably, in the above method for preparing a layered SiOx material, the specific operating parameters of the sintering in step (3) are as follows: the temperature rising speed is 1-10 ℃/min, the sintering temperature is 300-600 ℃, and the sintering atmosphere is N2Ar or H2One of the mixed gas/Ar atmosphere.
The beneficial effects of the above technical scheme are: and a large number of functional groups such as hydroxyl groups, hydrogen bonds and the like exist on the surface of the siloxene, and the surface functional groups can be removed by heat treatment in an inert atmosphere to obtain the SiOx material with a laminated structure. Specifically, the limitation of sintering temperature and time can ensure the generation of SiOx and can also prevent the disproportionation reaction of the SiOx generated at an over-high temperature; n is a radical of2Ar or H2The inert atmosphere of/Ar and the like can ensure that the silicon of the SiOx is not oxidized into the electrochemically inert SiO 2.
The invention also discloses an application of the layered SiOx material prepared by the method, wherein the layered SiOx material is directly used as a lithium ion battery cathode material; or the layered SiOx material is used as a negative electrode active material, is mixed with a conductive agent and a binder to be used as a negative electrode material, and is applied to a lithium ion battery consisting of a negative electrode, a positive electrode, a diaphragm and an electrolyte.
Compared with the prior art, the invention discloses a layered SiOx material and a preparation method thereof, and the layered SiOx material has the following advantages and beneficial effects:
1. the thickness of a single sheet of the laminated SiOx is 30-40nm, and the nano-scale thickness is beneficial to quickly releasing stress/strain caused by volume expansion; the interlayer nanometer slit has rich gaps, so that the contact area of the active material and the electrolyte can be increased, and the rapid transmission of lithium ions is facilitated; the interlayer gap can also accommodate the volume expansion of the silicon material, so that smaller particle-level outward volume expansion is generated, and the structural integrity of the electrode is maintained;
2. the preparation method is efficient and easy to implement, has simple operation steps, and can be completed only by two steps of etching and high-temperature calcination;
3. the prepared laminated SiOx material is suitable for being used as a lithium ion battery cathode material, and the electrochemical performance of the cathode material is tested, so that the laminated SiOx material in a half battery has excellent electrochemical performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an SEM image of a layered SiOx material of example 1 of the present invention;
FIG. 2 is a TEM image of a layered SiOx material of example 1 of the present invention;
FIG. 3 is a powder X-ray diffraction (XRD) pattern of the layered SiOx material of example 1 of the present invention;
FIG. 4 is an NMR chart of the layered SiOx material of example 1 of the present invention;
FIG. 5 is a first charging and discharging curve of the layered SiOx material of embodiment 1 of the present invention at a current density of 0.01-1.5V and 100 mA/g;
FIG. 6 is a rate performance curve of the layered SiOx material of embodiment 1 of the invention at 0.01-1.5V and at different current densities;
FIG. 7 is a cycle performance curve of the layered SiOx material of example 1 of the present invention at a current density of 200mA/g and a voltage of 0.01-1.5V;
FIG. 8 is a scanning electron microscope of the layered SiOx material of example 2 of the present invention;
FIG. 9 is a first three times charge and discharge curve of the layered SiOx material of example 2 of the present invention;
FIG. 10 is a graph of the cycling performance of the layered SiOx material of example 2 of the present invention at a current density of 100 mA/g;
FIG. 11 is a scanning electron microscope of the layered SiOx material of example 3 of the present invention;
FIG. 12 is a first three times charge and discharge curve of the layered SiOx material of example 3 of the present invention;
FIG. 13 is a graph of the cycling performance of the layered SiOx material of example 3 of the invention at a current density of 500 mA/g.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious 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.
Example 1
The preparation method of the layered SiOx material of the embodiment specifically includes the following steps:
(1) 2g of CaSi2Slowly adding 200ml of NaCl solution with the concentration of 10mol/L, and adding 200ml of CH with the concentration of 8mol/L at the speed of 1ml/min under the stirring speed of 800r/min3COOH, stirring and reacting for 3d, performing ultrasonic treatment for 1h under the power of 80W, washing for 4 times by using deionized water until the filtrate is neutral, and performing freeze drying for 12h to obtain a green layered siloxene material;
(2) weighing 1g of siloxene material, heating to 400 ℃ at the speed of 5 ℃/min in a tube furnace under the Ar atmosphere, preserving heat for 1h, and naturally cooling to room temperature to obtain the layered SiOx material.
The following tests were carried out on the layered SiOx material obtained in example 1 of the present invention:
the SEM image and TEM image of the SiOx material obtained in example 1 of the present invention are shown in fig. 1 and fig. 2, respectively, and it can be seen that the SiOx material is micron-sized particles and has a layered structure similar to an accordion, a large number of slit voids with nanometer-scale width exist between layers, and the thickness of a single sheet is about 30-40 nm.
The XRD characterization result of the layered SiOx material obtained in example 1 of the present invention is shown in fig. 3, and it can be seen that the layered material contains a certain amount of elemental silicon and FeSi2 in addition to amorphous SiOx, and elemental silicon and FeSi2 are derived from the process of preparing the raw material CaSi 2.
In order to determine the different chemical environments of Si in the layered SiOx material, the layered SiOx material prepared in example 1 of the present invention was subjected to solid-state nuclear magnetic characterization, and the 29Si MAS NMR characterization result is shown in fig. 4. Two distinct nuclear magnetic resonance peaks can be observed in the 29Si spectrum, the peak centered at-81 ppm chemical shift corresponding to covalent bonding of Si atoms to adjacent Si atoms in crystalline silicon, and the peak centered at-109 ppm chemical shift being the tetrahedrally coordinated silicon atom in the amorphous SiOx environment.
The electrochemical properties of the layered SiOx material obtained in example 1 of the present invention were tested as follows:
taking the prepared laminated SiOx material as an active substance, and mixing the active substance: conductive agent: the binder is mixed in a ratio of 8:1:1, wherein the conductive agent is conductive carbon black super P, the binder is CMC and SBR, and the mass ratio of the CMC to the SBR is 7: 3. after stirring uniformly, the coating is coated on a copper foil.
Drying the obtained pole piece at 80 ℃, compacting under certain pressure, continuously drying for 10 hours at 80 ℃, then cutting the pole piece into round sheets, taking a lithium sheet as a counter electrode, and taking LiPF with the concentration of 1mol/L6The EC + DMC (volume ratio 1: 1) solution of (A) was used as an electrolyte and assembled into an experimental cell in a glove box filled with argon.
The experimental battery adopts a Xinwei electrochemical test channel to carry out charge-discharge cycle test, the charge cut-off voltage is 1.50V, and the discharge cut-off voltage is 0.01V.
The results are shown in FIGS. 5-7:
fig. 5 is a first charge-discharge curve of the layered SiOx material. The result shows that the first reversible capacity of the laminated SiOx material is 740mAh/g, and the first coulombic efficiency is 42%.
FIG. 6 is a graph showing the rate capability of a layered SiOx material at 50mA g-1，100mA·g-1，200mA·g-1，500mA·g-1，1000mA·g-1，2000mA·g-1And 3000mA g-1Under multiplying power, the 10-cycle average reversible capacity of the laminated SiOx material is 744mAh g-1，715mAh·g-1，674mAh·g-1,602mAh·g-1，520mAh·g-1，396mAh·g-1And 210 mAh. g-1When the multiplying power is recovered to 50mA g-1When the reversible capacity is still 745mAh g-1And initial 50mA g-1The average capacity under the multiplying power is not different, and further shows the excellent capacity reversible characteristic.
FIG. 7 is a circulation performance curve of the layered SiOx material under the current density of 500mA/g, the first charge specific capacity under the current density of 500mA/g is 585.7mAh/g, the charge specific capacity after 160 cycles is 635.1mAh/g, and the capacity retention rate exceeds 100%, which indicates that the material has good circulation stability.
Example 2
The preparation method of the layered SiOx material of the embodiment specifically includes the following steps:
(1) 10g of CaSi2500ml of AlCl with the concentration of 10mol/L are slowly added3To the solution, 1000ml of HNO with a concentration of 10mol/L was added at a rate of 2ml/min with a stirring speed of 1000r/min3Stirring for reaction for 4d, performing ultrasonic treatment for 2h under 80W power, washing for 4 times by using deionized water until the filtrate is neutral, and performing freeze drying for 12h at-45 ℃ to obtain a siloxene material;
(2) weighing 5g of siloxene material, heating to 300 ℃ at the speed of 2 ℃/min in an Ar atmosphere in a tube furnace, preserving heat for 2h, and naturally cooling to room temperature to obtain the layered SiOx material.
The scanning electron microscope test of the material obtained in example 2 showed that the SiOx material had a layered structure and a large number of voids between the layers, as shown in fig. 8. According to the active substance: conductive agent: the binder is prepared by mixing the binder with the paste and the coating according to the proportion of 6:2:2, the constant current charge-discharge test is carried out on the binder, the first three charge-discharge curves of the SiOx material under the current density of 50mA/g are shown in figure 9, the results show that the reversible capacity of the first three charge-discharge of the layered SiOx material is 669mAh/g, 657mAh/g and 659mAh/g respectively, and the corresponding coulombic efficiencies are 39.8%, 89.6% and 93.5% respectively. FIG. 10 is a graph of cycling performance at a current density of 100mA/g, with a capacity of 693mAh/g after 50 cycles.
Example 3
The preparation method of the layered SiOx material of the embodiment specifically includes the following steps:
(1) 20g of CaSi2Slowly adding 400ml of NaCl solution with the concentration of 15mol/L, and adding 500ml of CH with the concentration of 12mol/L at the speed of 0.5ml/min under the stirring speed of 500r/min3CH2COOH, stirring and reacting for 4d, performing ultrasonic treatment for 3h under the power of 100W, washing for 4 times by using deionized water until the filtrate is neutral, and performing vacuum drying for 12h at the temperature of 100 ℃ to obtain a siloxene material;
(2) the siloxene material was placed in a tube furnace in H2Heating to 450 ℃ at the speed of 5 ℃/min under the Ar mixed atmosphere, preserving the heat for 1h, and naturally cooling to room temperature to obtain the SiOx material.
As a result of the sem test of the material obtained in example 3, the SiOx material had an accordion-like layered structure and a large number of voids were formed between the layers, as shown in fig. 11. According to the active substance: conductive agent: the binder is prepared by mixing the binder with the paste and the coating according to the ratio of 8:1:1, constant current charge and discharge tests are carried out on the binder, the first three charge and discharge curves of the SiOx material under the current density of 50mA/g are shown in figure 12, the results show that the reversible capacity of the first three charge and discharge of the layered SiOx material is 731mAh/g, 733mAh/g and 727mAh/g respectively, and the corresponding coulombic efficiencies are 42.5%, 91.1% and 97.5% respectively. FIG. 13 is a graph of the cycling performance at a current density of 500mA/g, with a capacity of 548mAh/g after 100 cycles.
According to the invention, the accordion-like laminated structure silicon material with the interlayer gap is obtained by controlling the concentration of HCl in the reaction system, and the interlayer gap can fully accommodate the volume change of the silicon material in the process of lithium desorption, so that the material prepared by the method can keep higher cycle stability in the process of charging and discharging, and the capacity is hardly attenuated.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
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 (10)
1. The laminated SiOx material is characterized in that the SiOx material is accordion-shaped laminated micron-sized particles, the particle size of the SiOx material is 0.5-20 mu m, slit gaps with nanoscale width exist between any two adjacent layers, the width of each slit gap is 1-50 nm, and the thickness of each single sheet layer is 30-40 nm.
2. The SiOx material of claim 1, wherein x in the SiOx material has a value in the range of 0< x < 2.
3. A method for the preparation of a layered SiOx material according to any one of claims 1-2, comprising the steps of:
(1) preparing a solution: and respectively dissolving the substance A and the substance B in deionized water to obtain a solution A and a solution B.
(2) Preparing a laminated siloxene material: mixing the solution A with CaSi2Sequentially adding the mixture into a reaction vessel, stirring the mixture until the mixture is uniformly mixed, adding the solution B, stirring the mixture for reaction for 1 to 4 days, ultrasonically oscillating the mixture for 0.5 to 5 hours, and washing the mixture for 3 to 10 times by using deionized waterDrying to obtain a laminated siloxene material;
(3) preparing a layered SiOx material: and sintering the layered siloxene material for 0.5-5h in an inert atmosphere to obtain the layered SiOx material.
4. The method of claim 3, wherein the substance A in step (1) is a chlorine-containing inorganic salt selected from NaCl, AlCl, etc3、MgCl2、KCl、LiCl、ZnCl2、CaCl2、CuCl2、FeCl3、CoCl2、NiCl2One or a mixture of a plurality of the components according to any proportion;
the substance B is HOOCCOOH, H2CO3、H2SO4、HNO3、H3PO4、HClO4、CH3COOH、CH3CH(OH)COOH、C6H8O7HCOOH and CH3CH2One or a mixture of more than one of COOH according to any proportion.
5. The method of claim 3 or 4, wherein the concentration of the solution A in the step (1) is 0.1-15 mol/L, and the concentration of the solution B in the step (1) is 0.1-12 mol/L.
6. The method of claim 3, wherein the CaSi in step (2) is added to the layered SiOx material2And solution a in a ratio of 1 g: (50-500) mL, wherein the volume ratio of the solution A to the solution B is 1: (0.5-2).
7. The method of claim 3, wherein the stirring speed in step (2) is 200 to 1000 r/min; the adding rate of the solution B is V/2000-V/300 per minute, wherein V is the total volume of the solution B.
8. The method for preparing the layered SiOx material according to claim 3, wherein the drying in step (2) is vacuum drying or freeze drying, wherein the vacuum drying temperature is 80-120 ℃, the freeze drying temperature is-35 to-50 ℃, and the drying time is 10-24 h.
9. The method of claim 3, wherein the sintering in step (3) is performed with the following parameters: the temperature rising speed is 1-10 ℃/min, the sintering temperature is 300-600 ℃, and the sintering atmosphere is N2Ar or H2One of the mixed gas/Ar atmosphere.
10. Use of the layered SiOx material prepared by the method according to any one of claims 3 to 9, wherein the layered SiOx material is directly used as a negative electrode material for a lithium ion battery; or the layered SiOx material is used as a negative electrode active material, and is mixed with a conductive agent and a binder to be used as a negative electrode to be applied to a lithium ion battery.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113488527A (en) * | 2021-07-21 | 2021-10-08 | 山东大学深圳研究院 | Silicon dioxide nanosheet and pressure control method preparation process and application thereof |
| CN113488376A (en) * | 2021-07-21 | 2021-10-08 | 山东大学深圳研究院 | Two-dimensional silicon dioxide and preparation method and application thereof |
| CN113540689A (en) * | 2021-07-16 | 2021-10-22 | 山东大学 | High-thermal-stability battery diaphragm and preparation method and application thereof |
| CN113571765A (en) * | 2021-07-23 | 2021-10-29 | 山东大学 | Two-dimensional silicon oxide composite PEO solid electrolyte, and preparation method and application thereof |
| CN113800523A (en) * | 2021-09-09 | 2021-12-17 | 哈尔滨工业大学 | Layered porous silicon material and preparation method and application thereof |
| CN114927662A (en) * | 2022-05-26 | 2022-08-19 | 哈尔滨工业大学 | Preparation method and application of sheet-shaped SiOx material with controllable oxygen content |
| CN115241428A (en) * | 2022-07-11 | 2022-10-25 | 哈尔滨工业大学 | 2D lamellar SiOx material performance regulation and control method and application thereof |
| CN115241428B (en) * | 2022-07-11 | 2024-05-10 | 哈尔滨工业大学 | 2D lamellar SiOx material performance regulation and control method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113540689A (en) * | 2021-07-16 | 2021-10-22 | 山东大学 | High-thermal-stability battery diaphragm and preparation method and application thereof |
| CN113488527A (en) * | 2021-07-21 | 2021-10-08 | 山东大学深圳研究院 | Silicon dioxide nanosheet and pressure control method preparation process and application thereof |
| CN113488376A (en) * | 2021-07-21 | 2021-10-08 | 山东大学深圳研究院 | Two-dimensional silicon dioxide and preparation method and application thereof |
| CN113488376B (en) * | 2021-07-21 | 2024-04-16 | 山东大学深圳研究院 | Two-dimensional silicon dioxide and preparation method and application thereof |
| CN113571765A (en) * | 2021-07-23 | 2021-10-29 | 山东大学 | Two-dimensional silicon oxide composite PEO solid electrolyte, and preparation method and application thereof |
| CN113571765B (en) * | 2021-07-23 | 2023-04-28 | 山东大学 | Two-dimensional silicon oxide composite PEO solid electrolyte and preparation method and application thereof |
| CN113800523A (en) * | 2021-09-09 | 2021-12-17 | 哈尔滨工业大学 | Layered porous silicon material and preparation method and application thereof |
| CN114927662A (en) * | 2022-05-26 | 2022-08-19 | 哈尔滨工业大学 | Preparation method and application of sheet-shaped SiOx material with controllable oxygen content |
| CN115241428A (en) * | 2022-07-11 | 2022-10-25 | 哈尔滨工业大学 | 2D lamellar SiOx material performance regulation and control method and application thereof |
| CN115241428B (en) * | 2022-07-11 | 2024-05-10 | 哈尔滨工业大学 | 2D lamellar SiOx material performance regulation and control method and application thereof |
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