CN114014320A - Method for preparing carbon-silicon composite material by using algae biomass and application of carbon-silicon composite material in lithium ion battery - Google Patents
Method for preparing carbon-silicon composite material by using algae biomass and application of carbon-silicon composite material in lithium ion battery Download PDFInfo
- Publication number
- CN114014320A CN114014320A CN202111369515.5A CN202111369515A CN114014320A CN 114014320 A CN114014320 A CN 114014320A CN 202111369515 A CN202111369515 A CN 202111369515A CN 114014320 A CN114014320 A CN 114014320A
- Authority
- CN
- China
- Prior art keywords
- carbon
- composite material
- silicon
- algae biomass
- lithium
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/023—Preparation by reduction of silica or free silica-containing material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
Abstract
The invention discloses a method for preparing a carbon-silicon composite material by using algae biomass and application of the carbon-silicon composite material in a lithium ion battery. The invention adopts a molten salt method, fully utilizes the algae biomass causing environmental pollution to prepare the carbon-silicon composite material, has simple process and low cost, and amorphous carbon formed by carbonizing carbon elements contained in the algae biomass precursor is uniformly and hierarchically compounded with silicon, thereby effectively improving the conductivity of the material.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of biological waste resources and the technical field of lithium ion batteries, and particularly relates to a method for preparing a carbon-silicon composite material by using algae biomass; the invention also relates to the application of the carbon-silicon composite material as a negative electrode material of a lithium ion battery.
Background
The occurrence of harmful algal blooms (including red tides and water blooms) is often reported around the world, with the consequent serious disruption of the world's ecosystem and extremely adverse effects on human society. Especially blue-green algae (cyanobacteria) produce toxins (neurotoxins, cytotoxins, endotoxins and hepatotoxins) that are serious threats to the life safety of humans, livestock and wild animals. The substances in which microcystins are released from cyanobacteria are considered carcinogens and can bioaccumulate in aquatic organisms (e.g., shellfish) in eutrophic water. A remarkable example is that toxic algae such as seasonal nested lakes, Yangtze lakes, Dongting lakes and the like are massively propagated to cause death of fishes, shrimps, crabs and shellfish, so that aquatic resources are greatly damaged, and the construction of ports and wharfs is seriously influenced due to the formation of sediments.
There are two types of methods for solving the environmental problem of harmful algal blooms. The first approach is to enhance prophylaxis; the second approach is to apply mitigation measures. The preventive measures are to prevent the eutrophication of the water body by controlling the runoff of urban and agricultural activities flowing into the water body, so as to inhibit the growth of algae. Methods of preventive measures are desirable, but as the demand for food increases with increasing agricultural production, preventive measures to control fertilizer loss become difficult. The problem cannot be solved by intensive precautions alone. Mitigation includes the use of chemicals (e.g., copper sulfate), biologically competitive and grazing species (e.g., diatoms) to remove or control algal blooms after algae formation. These methods are not desirable in the future due to the large use of chemicals and the introduction of other species, their entry into waterways and their potential negative impact on the environment. Therefore, other solutions to the algal bloom problem are very important and necessary. If we can prepare the produced harmful algae into high-value functional products (we call garbage to treasure), it will have great importance and influence the society and environment widely. Ideally, high value functional products can be used for energy storage and other applications, helping to push society towards the sustainable future of energy.
In recent years, lithium ion batteries have been widely used to provide power to various types of small portable electronic devices (e.g., smart phones, notebook computers, and camcorders). In addition, they have also been used in Hybrid Electric Vehicles (HEVs) and large energy storage areas. In 2008, the sales of lithium ion rechargeable batteries have reached $ 100 billion, and if successful applications in Hybrid Electric Vehicles (HEVs) or plug-in electric vehicles (PEVs) are possible, the sales will increase dramatically in a short time. In 2017, the department of science and technology of the state issues a special item of a key research and development plan of a new energy automobile, continues to implement the transformation of a relay drive technology deeply, and specifies that the energy density of a lithium ion battery is more than 300Wh/kg, which puts higher requirements on the materials of the battery.
As the demand for safe and reliable lithium ion batteries having large capacity, high power and rate capability is increasing, research to find new electrode materials to replace the currently used materials is being conducted worldwide. Lithium cobaltate (LiCoO) in positive electrode material2) Lithium iron phosphate (LiFePO)4) Ternary material (LiNi)xCoyMn1-x-yO2) The development of materials is mature, and the capacity is difficult to increase; thus, lithium sulfur (Li-S) batteries, lithium air (Li-O)2) Batteries have received a great deal of attention from researchers. Besides the anode material, finding a cathode material with higher specific capacity is also an effective method for improving the energy density and the power density of the lithium ion battery. Silicon (Si), germanium (Ge), tin (Sn) and the like which are elements of a fourth main group are regarded as anode materials with great prospects of Lithium Ion Batteries (LIBs) due to the ultrahigh specific capacity. The negative electrode material has an important influence on the capacity, energy density, cycle performance and the like of the lithium ion battery. As a lithium ion batteryShould have the following conditions: should have a low potential to match the positive electrode material and provide a high discharge voltage; when reacting with lithium, the crystal structure can not be changed significantly; the reaction is highly reversible; high lithium ion diffusion coefficient; high electron conductivity; proper compactness; a large amount of charge can be stored per unit mass.
Silicon (Si) has been widely studied for its excellent electrochemical properties, and has a relatively low voltage and an ultra-high theoretical specific capacity (the product at room temperature is Li)15Si43590 mAh g-1) About 10 times (about 372 mAh g) of the carbonaceous material-1). Silicon is abundant in the earth's crust and therefore relatively low in cost. However, there are some challenges when using silicon as LIBs negative electrodes, including its intrinsically poor conductivity, large volume change (about 300%), and instability of solid electrolyte membranes (SEI), which can lead to destruction of the electrode structure and loss of stored energy.
In general, it is necessary to coat carbon on nano Si in order to improve Li storage performance. In one aspect, the carbon-containing additive may serve as a matrix for buffering bulk changes in silicon during repeated lithium ion insertion/extraction: (>270%). On the other hand, the carbon component is advantageous for improving the conductivity of the electrode material. For example, silicon nanoparticles prepared from bamboo leaves, at 8.4A g-1At a current density of 430 mAh g only-1The reversible capacity of (a). After the silicon nano-particles are coated by carbon and redox graphene, 1400 mAh g can be obtained under the same current density-1The reversible specific capacity of (a). Obviously, the organic carbon content of silicon-containing natural biomass is typically burned off during the process of preparing silicon crystals. Therefore, it is highly desirable and necessary to take full advantage of the silicon and carbon elements of these sustainable, abundant natural products to make Si @ C composites.
Disclosure of Invention
The invention aims to solve the problem of resource utilization of harmful algae pollutants in red tide and water bloom, simultaneously utilizes carbon and silicon elements in algae biomass, and provides a molten salt method for preparing a carbon-silicon composite material by utilizing the algae biomass;
the invention also aims to provide application of the carbon-silicon composite material as a negative electrode material of a lithium ion battery.
Preparation of carbon-silicon composite material
The invention discloses a method for preparing a carbon-silicon (Si @ C) composite material by using algae biomass, which comprises the following steps of:
(1) fully mixing and stirring the algae biomass, water and dilute hydrochloric acid, filtering, washing and drying to obtain the algae biomass without inorganic salts; the algae biomass is algae pollutant salvaged in red tide or water bloom, and mainly comprises diatom, blue algae, first algae, green algae, yellow algae and naked algae.
(2) And crushing the algae biomass without the inorganic salt, and calcining and carbonizing the crushed algae biomass in air at 450-550 ℃ for 2-5 hours to obtain the silicon dioxide and carbon composite.
(3) Grinding the silicon dioxide and carbon composite into powder, adding metal powder and molten salt, uniformly grinding in an inert atmosphere, calcining at 300-700 ℃ for 8-12 h, and cooling the obtained product to room temperature and taking out. Wherein the metal powder is one of zinc powder, magnesium powder and aluminum powder; the molten salt is at least one of anhydrous lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, zinc chloride, aluminum chloride and potassium iodide.
The mole ratio of the silicon dioxide to the metal powder to the molten salt in the silicon dioxide and carbon composite is 1:1.8: 40-1: 2.3: 60. And (3) calcining a part of the composite of the silica and the carbon obtained in the step (2) in air to remove the carbon to obtain the mass of the silica, thereby obtaining the content of the silica in the composite of the silica and the carbon, and further calculating the molar quantity of the composite of the silica and the carbon added in the step.
(4) Adding dilute hydrochloric acid into the product obtained in the step (3), fully mixing, filtering, washing with water, drying, and removing a by-product magnesium oxide to obtain a carbon-silicon composite material; the concentration of the dilute hydrochloric acid is 0.1-4 mol/L, and then the dilute hydrochloric acid is subjected to suction filtration and drying; the drying is vacuum drying, and the drying temperature is 60-100 ℃.
Structure and performance of carbon-silicon composite material
1. Structure of carbon-silicon composite material
Fig. 1 is an XRD diffraction pattern of the carbon-silicon composite material prepared by the invention. From the XRD diffractogram of FIG. 1, it is clear that the three-intensity peaks at 28.5 °, 47.2 ° and 56.19 ° correspond well to cubic silicon (JPCDS number 27-1402), and no other impurity peaks are present.
Fig. 2 is an SEM image of the carbon-silicon composite material prepared by the present invention. As can be seen from the SEM image of fig. 2, the silicon nanoparticles are uniformly distributed in the carbon matrix, forming a uniform carbon-silicon micro-nano particle composite material.
FIG. 3 is a Raman spectrum of the carbon-silicon composite material prepared by the present invention. From the Raman spectrum of FIG. 3, it is found that the intensity of the Raman spectrum is about 520 cm-1Three significant peaks (Si crystals) are present; 1345 cm appears in the figure-1(band D, random carbon) and 1580 cm-1(G band, graphitization) two peaks.
2. Properties of carbon-silicon composite materials
The carbon-silicon composite material is used as a negative electrode material of the lithium ion battery. And assembling the carbon-silicon composite material and the electrolyte into the lithium ion battery. The electrolyte of the lithium ion battery is a mixed solution consisting of lithium salt and at least one of dimethyl carbonate, diethyl carbonate, ethylene carbonate, Biphenyl (BP), ethylene carbonate (VEC), Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), 1, 4-Butanesultone (BS), 1, 3-Propanesultone (PS), 1, 3- (1-Propylene) Sultone (PST), Ethylene Sulfate (ESA), Ethylene Sulfite (ESI), Cyclohexylbenzene (CHB), tert-butyl benzene (TBB), tert-amyl benzene (TPB) and Succinonitrile (SN); the lithium salt is lithium hexafluorophosphate (LiPF)6) Lithium bis (fluorosulfonamide) (LiFSI), lithium tetrafluoroborate (LiBF)4) Lithium bistrifluorosulfonamide (LiN (SO)2CF3)2) Lithium bis (oxalato) borate (LiBOB), lithium trifluoro methane sulfonate (LiSO)3CF3) At least one of (1).
FIG. 4 shows that the carbon-silicon composite material prepared by the present invention has a current density of 1.0CLong cycle performance at high temperatures. As can be seen from the cycle performance graph of fig. 4, the long cycle performance of the carbon silicon (Si @ C) composite was tested. The long cycle stability test of the carbon silicon (Si @ C) composite was performed at a current density of 1.0C and had 931.9 mAh g after 400 cycles-1Specific capacity of (2) is higher than the theoretical capacity (372 mAh g) of commercial graphite cathode-1) About three times higher.
Fig. 5 is a charge/discharge specific capacity-voltage curve of the carbon-silicon composite material prepared by the invention under the current density of 1C for different cycle times. Fig. 5 shows that the charge/discharge potential plateau curves for different turns at 1.0C current density overlap very well, indicating that the carbon silicon (Si @ C) composite has excellent cycling stability.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention fully utilizes the environmental pollution biomass, has simple process and low cost, greatly improves the production efficiency and safety, can fully meet the requirement of modern industrial production, realizes commercial large-scale production, and has wide application prospect.
2. The invention adopts a molten salt method, prepares the carbon-silicon composite electrode material by utilizing the algae biomass, and the amorphous carbon formed by carbonizing the carbon element contained in the algae biomass precursor is uniformly and hierarchically compounded with the silicon, thereby effectively improving the conductivity of the material.
3. The invention provides a universally applicable method, which can simply and quickly prepare the silicon-carbon composite electrode material from the biomass containing silicon-carbon by a molten salt method, and has wide application prospects in the fields of smart phones, notebook computers, portable cameras, green energy sources, aerospace and the like.
Drawings
Fig. 1 is an XRD diffraction pattern of the carbon-silicon composite material prepared by the invention.
Fig. 2 is an SEM image of the carbon-silicon composite material prepared by the present invention.
FIG. 3 is a Raman spectrum of the carbon-silicon composite material prepared by the present invention.
FIG. 4 shows the long cycle performance of the carbon-silicon composite material prepared by the present invention at a current density of 1C.
Fig. 5 is a charge/discharge specific capacity-voltage curve of the carbon-silicon composite material prepared by the invention under the current density of 1C for different cycle times.
Detailed Description
The invention prepares the carbon-silicon composite material by utilizing the algae biomass through a simple molten salt thermal method. The method is simple and economic, is easy for mass preparation, and is beneficial to comprehensive utilization of biological waste resources. The amorphous carbon formed by carbonizing the carbon element contained in the algae biomass precursor is uniformly and hierarchically compounded with silicon, so that the conductivity of the material is effectively improved, the volume expansion is relieved, and the integrity of the pole piece is maintained.
The preparation and properties of the carbon-silicon (Si @ C) composite material of the present invention will be further explained and illustrated with reference to the following specific examples.
Example 1
A preparation method of a carbon silicon (Si @ C) composite material comprises the following specific steps:
(1) fully mixing and stirring 20g of algae biomass, 500mL of water and 40mL0.5mol/L of dilute hydrochloric acid, filtering, washing with water and drying to obtain the algae biomass without inorganic salts;
(2) crushing the algae biomass without the inorganic salt, calcining the crushed algae biomass in a muffle furnace for 2 hours at 450 ℃ in an air atmosphere to obtain a black silicon dioxide and carbon composite, and calcining a part of silicon dioxide and carbon composite in the air to remove carbon to obtain the silicon dioxide with the content of 30.8 percent in the silicon dioxide and carbon composite;
(3) grinding the silicon dioxide and carbon composite obtained in the step (2) into powder according to the proportion of silicon dioxide: magnesium metal powder: AlCl3Adding magnesium metal powder and anhydrous AlCl into the molten salt according to the molar ratio of 1:2.2:503Melting salt, grinding in inert atmosphere, transferring into high temperature kettle, heating at 5 deg.C/minCalcining at 300 ℃ for 10h, cooling the obtained product to room temperature and taking out;
(4) transferring the product obtained in the step (3) to a beaker, adding 50-60 mL of 3mol/L diluted hydrochloric acid, fully mixing, filtering, washing with water, drying, and removing a byproduct magnesium oxide to obtain a carbon-silicon (Si @ C) composite material;
(5) taking the carbon-silicon (Si @ C) composite material obtained in the step (4) as a negative electrode, taking the combination of ethylene carbonate and dimethyl carbonate as electrolyte, and lithium hexafluorophosphate (LiPF)6) And (5) assembling the lithium ion battery as a lithium salt. At the current density of 1.0C, after 400 cycles, the capacity is 517mAh g-1。
Example 2
A preparation method of a carbon silicon (Si @ C) composite material comprises the following specific steps:
(1) fully mixing and stirring 20g of algae biomass, 500mL of water and 40mL0.5mol/L of dilute hydrochloric acid, filtering, washing with water and drying to obtain the algae biomass without inorganic salts;
(2) crushing the algae biomass without the inorganic salts, calcining the crushed algae biomass in a muffle furnace at 500 ℃ in an air atmosphere for 2 hours to obtain a black silicon dioxide and carbon composite, and calcining a part of silicon dioxide and carbon composite in the air to remove carbon to obtain the silicon dioxide with the content of 33.4 percent in the silicon dioxide and carbon composite;
(3) grinding the product obtained in step (2) into a powder, according to the weight ratio of silicon dioxide: magnesium metal powder: ZnCl2Adding magnesium metal powder and anhydrous ZnCl into molten salt according to the molar ratio of 1:2.2:502Melting salt, grinding uniformly in an inert atmosphere, transferring into a high-temperature kettle, heating to 300 ℃ at a heating rate of 5 ℃/min, calcining for 10h, cooling the obtained product to room temperature, and taking out;
(4) transferring the product obtained in the step (3) into a beaker, adding 50-60 mL of 3mol/L diluted hydrochloric acid, fully mixing, filtering, washing with water, drying, and removing a byproduct magnesium oxide to obtain a carbon-silicon (Si @ C) composite material;
(5) taking the carbon-silicon (Si @ C) composite material obtained in the step (4) as a negative electrode, taking the combination of ethylene carbonate and dimethyl carbonate as electrolyte, and lithium hexafluorophosphate (L)iPF6) And (5) assembling the lithium ion battery as a lithium salt. The capacity is 689 mAh g after 400 cycles under the current density of 1.0C-1。
Example 3
A preparation method of a carbon silicon (Si @ C) composite material comprises the following specific steps:
(1) fully mixing and stirring 20g of algae biomass, 500mL of water and 40mL0.5mol/L of dilute hydrochloric acid, filtering, washing with water and drying to obtain the algae biomass from which inorganic salts are removed;
(2) crushing the algae biomass without the inorganic salt, calcining the crushed algae biomass in a muffle furnace at 500 ℃ in an air atmosphere for 3 hours to obtain a black silicon dioxide and carbon composite, and calcining a part of silicon dioxide and carbon composite in the air to remove carbon to obtain the silicon dioxide with the content of 30.7 percent in the silicon dioxide and carbon composite;
(3) grinding the product obtained in step (2) into a powder, according to the weight ratio of silicon dioxide: aluminum metal powder: AlCl3Adding aluminum metal powder and anhydrous AlCl into molten salt according to the molar ratio of 1:1.8:503Melting salt, grinding uniformly in an inert atmosphere, transferring into a high-temperature kettle, heating to 300 ℃ at a heating rate of 5 ℃/min, calcining for 10h, cooling the obtained product to room temperature, and taking out;
(4) transferring the product obtained in the step (3) to a beaker, adding 50-60 mL of 3mol/L diluted hydrochloric acid, fully mixing, filtering, washing with water, drying, removing by-products such as magnesium oxide and the like, and repeatedly performing to obtain the carbon-silicon (Si @ C) composite material;
(5) taking the carbon-silicon (Si @ C) composite material obtained in the step (4) as a negative electrode, taking the combination of ethylene carbonate and dimethyl carbonate as electrolyte, and lithium hexafluorophosphate (LiPF)6) And (5) assembling the lithium ion battery as a lithium salt. Under the current density of 1.0C, after 400 cycles, the capacity is 816mAh g-1。
Example 4
A preparation method of a carbon silicon (Si @ C) composite material comprises the following specific steps:
(1) fully mixing and stirring 20g of algae biomass, 500mL of water and 40mL0.5mol/L of dilute hydrochloric acid, filtering, washing with water and drying to obtain the algae biomass from which inorganic salts are removed;
(2) crushing the algae biomass without the inorganic salt, calcining the crushed algae biomass in a muffle furnace at 500 ℃ in an air atmosphere for 3 hours to obtain a black silicon dioxide and carbon composite, and calcining a part of silicon dioxide and carbon composite in the air to remove carbon to obtain the silicon dioxide with the content of 32.3 percent in the silicon dioxide and carbon composite;
(3) grinding the product obtained in step (2) into a powder, according to the weight ratio of silicon dioxide: magnesium metal powder: AlCl3Adding magnesium metal powder and anhydrous AlCl into the molten salt according to the molar ratio of 1:2.2:503Melting salt, grinding uniformly in an inert atmosphere, transferring into a high-temperature kettle, heating to 300 ℃ at a heating rate of 5 ℃/min, calcining for 10h, cooling the obtained product to room temperature, and taking out;
(4) transferring the product obtained in the step (3) to a beaker, adding 50-60 mL of 3mol/L diluted hydrochloric acid, fully mixing, filtering, washing with water, drying, removing by-products such as magnesium oxide and the like, and repeatedly performing to obtain the carbon-silicon (Si @ C) composite material;
(5) taking the carbon-silicon (Si @ C) composite material obtained in the step (4) as a negative electrode, taking the combination of ethylene carbonate and dimethyl carbonate as electrolyte, and lithium hexafluorophosphate (LiPF)6) And (5) assembling the lithium ion battery as a lithium salt. At a current density of 1.0C, after 400 cycles, the capacity was 788 mAh g-1。
Example 5
A preparation method of a carbon silicon (Si @ C) composite material comprises the following specific steps:
(1) fully mixing and stirring 20g of algae biomass, 500mL of water and 40mL0.5mol/L of dilute hydrochloric acid, filtering, washing with water and drying to obtain the algae biomass without inorganic salts;
(2) crushing the algae biomass without the inorganic salt, calcining the crushed algae biomass in a muffle furnace at 550 ℃ in an air atmosphere for 5 hours to obtain a black silicon dioxide and carbon composite, and calcining a part of silicon dioxide and carbon composite in the air to remove carbon to obtain the silicon dioxide with the content of 30.8 percent in the silicon dioxide and carbon composite;
(3) grinding the product obtained in step (2) into a powder, according to the weight ratio of silicon dioxide: magnesium metal powder: AlCl3Adding magnesium metal powder and anhydrous AlCl into the molten salt according to the molar ratio of 1:2.2:503Melting salt, grinding uniformly in an inert atmosphere, transferring into a high-temperature kettle, heating to 300 ℃ at a heating rate of 5 ℃/min, calcining for 10h, cooling the obtained product to room temperature, and taking out;
(4) transferring the product obtained in the step (3) to a beaker, adding 50-60 mL of 3mol/L diluted hydrochloric acid, fully mixing, filtering, washing with water, drying, removing by-products such as magnesium oxide and the like, and repeatedly performing to obtain the carbon-silicon (Si @ C) composite material;
(5) taking the carbon-silicon (Si @ C) composite material obtained in the step four as a negative electrode, taking the combination of ethylene carbonate and dimethyl carbonate as electrolyte, and lithium hexafluorophosphate (LiPF)6) And (5) assembling the lithium ion battery as a lithium salt. At a current density of 1.0C, after 400 cycles, the capacity was 931.9 mAh g-1。
Claims (8)
1. A method for preparing a carbon-silicon composite material by using algae biomass comprises the following steps:
(1) fully mixing and stirring the algae biomass, water and dilute hydrochloric acid, filtering, washing and drying to obtain the algae biomass without inorganic salts;
(2) crushing the algae biomass without the inorganic salt, and calcining and carbonizing the crushed algae biomass in air at 450-550 ℃ for 2-5 hours to obtain a silicon dioxide and carbon composite;
(3) grinding the silicon dioxide and carbon composite into powder, adding metal powder and molten salt, uniformly grinding in an inert atmosphere, calcining at 300-700 ℃ for 8-12 h, cooling the obtained product to room temperature, and taking out;
(4) and (4) adding dilute hydrochloric acid into the product obtained in the step (3), fully mixing, filtering, washing with water, drying, and removing a by-product magnesium oxide to obtain the carbon-silicon composite material.
2. The method for preparing the carbon-silicon composite material by using the algae biomass as claimed in claim 1, wherein the method comprises the following steps: in the step (3), the metal powder is one of zinc powder, magnesium powder and aluminum powder.
3. The method for preparing the carbon-silicon composite material by using the algae biomass as claimed in claim 1, wherein the method comprises the following steps: in the step (3), the molten salt is at least one of anhydrous lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, zinc chloride, aluminum chloride and potassium iodide.
4. The method for preparing the carbon-silicon composite material by using the algae biomass as claimed in claim 1, wherein the method comprises the following steps: in the step (3), the molar ratio of the silicon dioxide, the metal powder and the molten salt in the silicon dioxide and carbon composite is 1:1.8: 40-1: 2.3: 60.
5. The method for preparing the carbon-silicon composite material by using the algae biomass as claimed in claim 1, wherein the method comprises the following steps: in the step (4), the concentration of the dilute hydrochloric acid is 0.1-5 mol/L, and then the dilute hydrochloric acid is filtered and dried.
6. The method for preparing the carbon-silicon composite material by using the algae biomass as claimed in claim 1, wherein the method comprises the following steps: in the step (4), the drying is vacuum drying, and the drying temperature is 60-100 ℃.
7. An application of the carbon-silicon composite material prepared by the method of any one of claims 1 to 6 as a negative electrode material of a lithium ion battery.
8. The use of the carbon-silicon composite material according to claim 7 as a negative electrode material for lithium ion batteries, characterized in that: the electrolyte of the lithium ion battery is a mixed solution consisting of lithium salt and at least one of dimethyl carbonate, diethyl carbonate, ethylene carbonate, biphenyl, ethylene carbonate, vinylene carbonate, fluoroethylene carbonate, 1, 4-butyl sultone, 1, 3-propane sultone, 1, 3- (1-propylene) sultone, vinyl sulfate, ethylene sulfite, cyclohexylbenzene, tert-butyl benzene, tert-amyl benzene and succinonitrile; the lithium salt is at least one of lithium hexafluorophosphate, lithium bifluorosulfonamide, lithium tetrafluoroborate, lithium bistrifluorosulfonamide, lithium bisoxalato borate and lithium trifluoromethanesulfonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111369515.5A CN114014320A (en) | 2021-11-18 | 2021-11-18 | Method for preparing carbon-silicon composite material by using algae biomass and application of carbon-silicon composite material in lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111369515.5A CN114014320A (en) | 2021-11-18 | 2021-11-18 | Method for preparing carbon-silicon composite material by using algae biomass and application of carbon-silicon composite material in lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114014320A true CN114014320A (en) | 2022-02-08 |
Family
ID=80065068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111369515.5A Pending CN114014320A (en) | 2021-11-18 | 2021-11-18 | Method for preparing carbon-silicon composite material by using algae biomass and application of carbon-silicon composite material in lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114014320A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115465864A (en) * | 2022-10-26 | 2022-12-13 | 南京林业大学 | Nano silicon material prepared by low-temperature molten salt thermal method and preparation method and application thereof |
| CN116154197A (en) * | 2023-04-24 | 2023-05-23 | 西子清洁能源装备制造股份有限公司 | Biomass modified all-vanadium redox flow battery electrode and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5449505A (en) * | 1993-08-19 | 1995-09-12 | Rockwell International Corporation | Method for disposing of radioactive graphite and silicon carbide in graphite fuel elements |
| CN103951177A (en) * | 2014-04-21 | 2014-07-30 | 深圳市三鑫精美特玻璃有限公司 | Processing method for reinforcing special high-aluminium glass |
| CN104617275A (en) * | 2015-02-11 | 2015-05-13 | 武汉科技大学 | Method for preparing silicon-carbon compound from silicon-containing biomass as raw material as well as prepared silicon-carbon compound and application thereof |
| CN105413625A (en) * | 2015-12-31 | 2016-03-23 | 天津中科云健康装备科技有限公司 | Application of porous silicon dioxide to metal filtration |
| CN105600794A (en) * | 2015-12-31 | 2016-05-25 | 天津中科云健康装备科技有限公司 | Porous silicon dioxide and preparation method thereof |
| CN105932240A (en) * | 2016-05-11 | 2016-09-07 | 武汉科技大学 | Nano-silicon-carbon compound and preparation method and application thereof |
| CN108682817A (en) * | 2018-05-21 | 2018-10-19 | 北京工业大学 | A kind of porous silicon-carbon cathode material preparation method for lithium ion battery |
| US20180317496A1 (en) * | 2014-02-19 | 2018-11-08 | Corning Incorporated | Antimicrobial glass compositions, glasses and polymeric articles incorporating the same |
| EP3470457A1 (en) * | 2017-10-10 | 2019-04-17 | Continental Reifen Deutschland GmbH | Sulphur-linkable rubber compound, vulcanizate of the rubber compound and vehicle tyres |
-
2021
- 2021-11-18 CN CN202111369515.5A patent/CN114014320A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5449505A (en) * | 1993-08-19 | 1995-09-12 | Rockwell International Corporation | Method for disposing of radioactive graphite and silicon carbide in graphite fuel elements |
| US20180317496A1 (en) * | 2014-02-19 | 2018-11-08 | Corning Incorporated | Antimicrobial glass compositions, glasses and polymeric articles incorporating the same |
| CN103951177A (en) * | 2014-04-21 | 2014-07-30 | 深圳市三鑫精美特玻璃有限公司 | Processing method for reinforcing special high-aluminium glass |
| CN104617275A (en) * | 2015-02-11 | 2015-05-13 | 武汉科技大学 | Method for preparing silicon-carbon compound from silicon-containing biomass as raw material as well as prepared silicon-carbon compound and application thereof |
| CN105413625A (en) * | 2015-12-31 | 2016-03-23 | 天津中科云健康装备科技有限公司 | Application of porous silicon dioxide to metal filtration |
| CN105600794A (en) * | 2015-12-31 | 2016-05-25 | 天津中科云健康装备科技有限公司 | Porous silicon dioxide and preparation method thereof |
| CN105932240A (en) * | 2016-05-11 | 2016-09-07 | 武汉科技大学 | Nano-silicon-carbon compound and preparation method and application thereof |
| EP3470457A1 (en) * | 2017-10-10 | 2019-04-17 | Continental Reifen Deutschland GmbH | Sulphur-linkable rubber compound, vulcanizate of the rubber compound and vehicle tyres |
| CN108682817A (en) * | 2018-05-21 | 2018-10-19 | 北京工业大学 | A kind of porous silicon-carbon cathode material preparation method for lithium ion battery |
Non-Patent Citations (3)
| Title |
|---|
| SELVA BILGE ET AL.: "Green synthesis of carbon based biosensor materials from algal biomass for the sensitive detection of vardenafil" * |
| ZHAO, ZQ ET AL.: "A Natural Transporter of Silicon and Carbon: Conversion of Rice Husks to Silicon Carbide or Carbon-Silicon Hybrid for Lithium-Ion Battery Anodes via a Molten Salt Electrolysis Approach", 《BATTERIES & SUPERCAPS》 * |
| 李恩雨: "MnO2/C材料在硝酸熔盐中的超级电容性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115465864A (en) * | 2022-10-26 | 2022-12-13 | 南京林业大学 | Nano silicon material prepared by low-temperature molten salt thermal method and preparation method and application thereof |
| CN116154197A (en) * | 2023-04-24 | 2023-05-23 | 西子清洁能源装备制造股份有限公司 | Biomass modified all-vanadium redox flow battery electrode and preparation method and application thereof |
| CN116154197B (en) * | 2023-04-24 | 2023-08-11 | 西子清洁能源装备制造股份有限公司 | Biomass modified all-vanadium redox flow battery electrode and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103435105B (en) | A kind of ferriferous oxide/carbon composition lithium ion battery cathode material and its preparation method and application | |
| WO2021114401A1 (en) | Iron-based sodium ion battery positive material, manufacturing method therefor, and sodium ion full battery | |
| CN111048770B (en) | Ternary doped silicon-based composite material and preparation method and application thereof | |
| CN109449379B (en) | Nitrogen-doped carbon composite SnFe2O4Lithium ion battery cathode material and preparation method and application thereof | |
| CN102104143A (en) | Hydrothermal synthesis method of composite material for high-performance power battery | |
| CN104009252A (en) | Sodium-ion battery and preparation method thereof | |
| CN106960954A (en) | A kind of preparation method and application of Prussian blue/graphene/sulphur composite | |
| CN114014320A (en) | Method for preparing carbon-silicon composite material by using algae biomass and application of carbon-silicon composite material in lithium ion battery | |
| CN104993125A (en) | Preparation method of lithium ion battery novel cathode material Fe3O4/Ni/C | |
| CN108346775B (en) | Metallic lithium negative electrode protected by shell-like structure | |
| CN103594708B (en) | One is appraised at the current rate iron-based composite positive pole and preparation method thereof | |
| CN102751489B (en) | Method for preparing anode material of lithium ion battery | |
| CN103000874A (en) | Preparation method of carbon-coated ternary positive electrode material | |
| KR101959761B1 (en) | Manufacturing method of cathode active material, and cathode active material for lithium secondary battery manufactured thereby | |
| CN113659143A (en) | Preparation method of negative electrode material of sodium ion battery, negative electrode material and sodium ion battery | |
| CN106898754B (en) | Application of heteroatom in preparation of carbon-phosphorus material of lithium-phosphorus battery, material and preparation method thereof | |
| Guo et al. | ZnO–SnO2/graphene composites as high capacity anode materials for lithium ion batteries | |
| CN102311109A (en) | Method for preparing LiFePO4/C composite cathode material by continuous reaction | |
| CN109411706B (en) | Modified working electrode and preparation method thereof | |
| CN107959024B (en) | Flaky Sb for sodium ion battery cathode2Se3Method for preparing nanocrystalline | |
| Liu et al. | Research progress on preparation and purification of fluorine-containing chemicals in lithium-ion batteries | |
| Bai et al. | High rate cyclability of nickle-doped LiNi 0.1 Mn 1.9 O 4 cathode materials prepared by a facile molten-salt combustion method for lithium-ion batteries | |
| CN115188936A (en) | Pre-lithiated binary topological structure phosphorus/carbon composite material and preparation method and application thereof | |
| CN114695881B (en) | Bismuth sulfide anode material and preparation method and application thereof | |
| CN113603141B (en) | Composite positive electrode material, 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 |