CN114068895B - Lignin-based graphene porous carbon nanosheet tin dioxide composite material and preparation and application thereof - Google Patents

Lignin-based graphene porous carbon nanosheet tin dioxide composite material and preparation and application thereof Download PDF

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CN114068895B
CN114068895B CN202111259379.4A CN202111259379A CN114068895B CN 114068895 B CN114068895 B CN 114068895B CN 202111259379 A CN202111259379 A CN 202111259379A CN 114068895 B CN114068895 B CN 114068895B
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易聪华
蒋勇
杨东杰
钱勇
庞煜霞
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South China University of Technology SCUT
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Abstract

The invention discloses a lignin-based graphene porous carbon nanosheet tin dioxide composite material and preparation and application thereof. The method of the invention is completed by two steps: taking water-soluble sulfonated lignin as a carbon precursor and a dispersing agent, taking basic magnesium carbonate as a template agent and an activating agent, taking water as a solvent, carrying out self-assembly under heating and stirring to obtain a uniformly dispersed compound, and then carrying out carbonization and acid washing to obtain a lignin-based graphene porous carbon nanosheet which is regular in structure, rich in oxygen-containing functional groups and hierarchical porous in structure; the carbon nano-sheet is used as a carbon skeleton and reacts with stannous salt under hydrothermal condition to obtain nano SnO 2 Growing in situ on the composite of the pore canal and the surface of the lignin porous carbon nano sheet. The invention solves the problem of SnO 2 The lithium ion battery cathode material has the problems of serious volume expansion and poor conductivity, and improves the specific capacity, the first coulombic efficiency and the rate capability of the lithium ion battery.

Description

Lignin-based graphene porous carbon nanosheet tin dioxide composite material and preparation and application thereof
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and particularly relates to a lignin-based graphene porous carbon nanosheet tin dioxide composite material, and preparation and application thereof.
Background
The development of new energy automobiles, aerospace and other fields has higher and higher requirements on the capacity and energy density of lithium ion power batteries. Graphite is used as a negative electrode material of a current commercial Lithium Ion Battery (LIB), and the theoretical capacity is only 372mAh g -1 The performance is poor under the heavy current density, and lithium dendrite is easy to appear after long-term circulation, which not only affects the service life of the lithium ion battery, but also reduces the safety of the lithium ion battery. Therefore, the development of high-capacity and high-safety lithium ion battery cathode materials is urgent.
Metal oxides such as titanium dioxide (TiO) 2 ) Manganese oxide (MnO, mn) 3 O 4 ，Mn 2 O 3 ，MnO 2 ) Iron oxide (Fe) 3 O 4 ，Fe 2 O 3 ) Cobaltosic oxide (Co) 3 O 4 ) Nickel oxide (NiO), zinc oxide (ZnO), tin dioxide (SnO) 2 ) And the like have been widely studied due to their higher theoretical capacity. SnO compared to other metal oxides 2 Has lower working potential (average discharge potential of 0.3V and average charge potential of 0.5V), is favorable for improving the energy density of the whole battery and avoiding the formation of lithium dendrites, and in addition, snO 2 The lithium ion battery cathode material has the advantages of low price, no toxicity, environmental friendliness and the like, and is expected to become a next-generation high-performance lithium ion battery cathode material. SnO 2 The theoretical lithium storage capacity of (b) is 1494mAh g -1 The lithium storage mechanism is divided into two steps:
SnO 2 +4Li + +4e - →Sn+2Li 2 O ①
Figure GDA0003398150730000011
wherein (1) is a conversion reaction, usually an irreversible reaction (for large particles of SnO 2 ) Or partially reversible reactions (for nano SnO) 2 ) Contribution 781mAh · g -1 Capacity of (2) an alloying reaction, usually a reversible reaction, contributing 783mAh g -1 The capacity of (c). Current limitation of SnO 2 The key problems in lithium battery negative electrode applications are: (1) Irreversible formation of SnO by reaction (1) 2 High irreversible capacity; (2) In the reaction (2), in the charging and discharging process, the volume change is large (about 300 percent), so that Sn is continuously agglomerated and pulverized, and an active substance and a current collector fall off, so that the capacity is rapidly attenuated, and the cycle performance is poor; (3) SnO 2 Low electronic conductivity and poor rate performance.
In view of the above problems, the solutions proposed by researchers are mainly divided into the following two types: (1) For SnO 2 Design of nano microstructure and construction of nano SnO with multidimensional structure 2 The nano size is beneficial to improving the reversible degree of the reaction (1) so as to improve the reversible capacity, and in addition, the nano size and the multi-dimensional structure have synergistic effect to effectively relieve SnO 2 The volume effect in the charging and discharging process improves the cycle stability and is beneficial to shortening Li + And the diffusion distance of electrons, and the rate capability is improved. Lou et al (Nanoscale, 2011,3 (9): 3586.) prepared SnO under hydrothermal conditions using sulfonated polystyrene microspheres (sPSHS) as a template 2 The composite with nano-sheets growing on sPSHS is finally formed by SnO through calcination under air condition 2 Hollow spherical structure formed by assembling nano sheets, and SnO with multi-dimensional structure 2 At 160mA · g -1 The reversible capacity of 519mAh g is obtained after 50 times of lower circulation -1 While SnO is performed under the same conditions 2 Nanoparticles and SnO 2 The capacity of the nanoflower is 391 and 269mAh g -1 . Although the nano microstructure design relieves the volume expansion and pulverization to some extent, the nano SnO 2 The electrode still can be agglomerated and pulverized after long-term circulation, so that the rapid attenuation of the circulation capacity is caused. (2) Mixing nano SnO 2 Is introduced into a conductive carbon skeleton (carbon nano tube, graphene, porous carbon and the like) to construct SnO 2 /C complex, effective in inhibiting SnO 2 The volume expansion of the composite material improves the conductivity of the composite material, thereby improving the lithium storage performance of the composite material. Among them, graphene is the most commonly used nano-loaded SnO 2 The conductive carbon skeleton has the advantages of high specific surface area, high conductivity, high mechanical strength and high flexibility, and the graphene is used as the carbon skeleton to construct the high-performance SnO 2 The/graphene composite lithium battery negative electrode has been widely researched. Utilizing graphene oxideThe carboxyl and hydroxyl functional groups on the surface can induce SnO 2 In-situ nucleation and growth to realize SnO 2 The graphene is uniformly dispersed on the surface of graphene, the particle size is controllable, and SnO is effectively inhibited 2 Aggregation and stacking of nanoparticles. Li et al (Journal of Materials Chemistry A,2014,2 (40): 17139) Graphene Oxide (GO) and SnCl 4 By modified colloidal solidification of the starting material and subsequent H 2 Atmosphere reduction to prepare reduced graphene oxide (rGO) and SnO 2 Composite (rGO/SnO) 2 ) In which the superfine nano SnO 2 (about 5 nm) uniformly distributed on rGO, rGO/SnO 2 At 1 A.g -1 The reversible capacity of 600 times of lower circulation is up to 795mAh g -1 . Guo et al (Journal of Power Sources,2014,262 4 The raw material urea is a precipitator and a reducing agent to prepare monodisperse rGO/SnO 2 In which nano SnO 2 (5 nm) anchored in situ and uniformly dispersed on GO at 0.5 A.g -1 The reversible capacity of 400 times of lower circulation is up to 1036mAh g -1 . Anchoring SnO by taking graphene as carbon skeleton 2 SnO with high performance can be obtained 2 Base lithium battery negative electrode material rGO/SnO 2 In general, the preparation method is generally divided into the following three steps: firstly, taking graphite or graphene as a raw material, and obtaining graphene oxide dispersion liquid by chemical oxidation with a strong oxidant; then dispersing tin salt into graphene oxide dispersion liquid to prepare GO/SnO 2 (ii) a Finally, reducing the GO in a reducing atmosphere at high temperature or by using a reducing agent to obtain rGO/SnO 2 And (3) a compound. However, the harsh conditions and high cost of graphene oxide preparation limit this rGO/SnO 2 Development and application of the same. Therefore, a simple and green way needs to be developed to prepare a two-dimensional (2D) carbon nanosheet with a graphene-like structure and rich in oxygen-containing functional groups such as hydroxyl and carboxyl on the surface, so as to replace graphene as anchoring SnO 2 Thereby realizing carbon nanosheet/SnO 2 And preparing the composite high-performance lithium battery cathode.
In recent years, researchers are interested in preparing sheet-shaped carbon materials with graphene-like structures by using biomass resources as raw materials. Lignin is a natural organic high molecular polymer with the second most abundant content on earth,is the only renewable aromatic polymer in natural plants. Industrial lignin is a major byproduct of pulp making, paper making, or biorefinery, with annual yields of about 5000 million tons, with only about 10% of the industrial lignin being used as a high efficiency water reducer or dispersant, most of which is burned as waste or low value fuel. The lignin is composed of guaiacyl, syringyl and p-hydroxyphenyl phenylpropane structural units, the carbon content in molecules is about 60%, and the structure contains a large number of oxygen-containing functional groups such as hydroxyl, carboxyl and the like, so that the lignin is an ideal carbon material precursor. By regulating and controlling the structure of lignin, the two-dimensional graphene sheet-shaped porous carbon is prepared as the loaded SnO 2 The carrier of (1), wherein oxygen-containing functional groups such as carboxyl groups, hydroxyl groups and the like remaining on the porous structure, lignin sheet-shaped char can induce SnO 2 To realize the nucleation and growth of SnO 2 The graphene sheet-shaped porous carbon can effectively inhibit SnO 2 The volume expansion and pulverization are carried out in the charging and discharging processes, thereby obtaining the lignin-based graphene flake porous carbon/SnO with high performance 2 The lithium battery negative electrode material.
The common preparation methods of the lignin-based graphene sheet carbon mainly comprise a solvent hydrophobic self-assembly method, a freeze casting method and a template method, and relevant published patents or literature analyses are as follows: wang et al (International Journal of Biological Macromolecules,2019, 128) dissolve sodium lignosulfonate in water, add acetone, which is a poor solvent, drop by drop to form sodium lignosulfonate nanosheets through hydrophobic self-assembly, and finally carbonize at high temperature to form lignin-based graphene carbon nanosheets. Such self-assembly methods typically involve volatile organic solvents to induce assembly and precipitation, and have low yields and are not suitable for large-scale preparation. Liu et al (RSC Advances,2017,7 (77): 48537) dissolve a certain amount of water-soluble alkali lignin in water, and place the solution in liquid nitrogen for quick freezing, freeze drying and carbonization to obtain a graphene-like carbon nanosheet with high microporosity; liu et al (ChemElectrochem, 2019,6 (15): 3949) prepared graphene-like sheet carbons of high specific surface area and high microporosity by dispersing low molecular weight (6000) alkali lignin and KOH in ultrapure water, rapidly freezing under liquid nitrogen, and then freeze-drying and carbonizing. Preparation by chill castingThe carbon nano sheet is generally low in specific surface area and high in microporosity, needs strong corrosive reagents such as KOH for secondary activation, and is not suitable for being used as supported SnO 2 The carbon skeleton of (2). The template method is most commonly used for synthesizing graphene-like carbon nanosheets, and commonly used templates comprise NaCl and H 3 BO 3 Oxalate salts, and the like. Xie et al (Advanced Powder Technology,30 (1): 170) use sodium lignosulfonate as a carbon precursor and NaCl as a template, and prepare the lignin-based porous carbon nanosheet through KOH post-activation. Wu et al (New Journal of Chemistry 2020,44 (48): 21271) use sodium lignosulfonate as carbon source, H 3 BO 3 And (3) preparing the lignin-based porous carbon nanosheet through KOH post-activation as a template. With NaCl and H 3 BO 3 The lignin-based graphene porous carbon nanosheet obtained by directly carbonizing the template generally has a smaller specific surface area, needs to be activated and carbonized again under the action of a KOH strong corrosive agent to obtain the carbon nanosheet with a high specific surface area and high microporosity, and is not suitable for being used as loaded SnO 2 The carbon skeleton of (2). Chinese patent CN 109485029B discloses a method for preparing lignin graphene porous carbon nano-sheets by combining a self-assembly method and a template method, wherein the lignin graphene porous carbon nano-sheets are prepared by performing layer-by-layer self-assembly on sulfonated lignin and oxalate in a selective solvent, carbonizing and acid washing, and the obtained carbon nano-sheets have high specific surface area and hierarchical porous structures due to the gas phase stripping and in-situ template action of oxalate, and the hierarchical porous structures and surface oxygen-containing functional groups can provide more SnO 2 The loading sites, however, require multiple iterations of this assembly, consume large amounts of ethanol organic reagents, and are complicated to operate and produce in low yields.
Lignin porous carbon and SnO 2 The preparation of complexes is relatively rare and has been analyzed as follows: cao et al (Electrochimica Acta,2020,345, 136172) have a core layer of lignin-Polymethylmethacrylate (PMMA), polyvinylpyrrolidone (PVP) -SnCl 2 ·2H 2 Preparing lignin-based multi-channel carbon fiber/SnO with core-shell structure by taking O as shell layer through coaxial co-electrospinning and carbonization 2 A composite wherein the mass ratio of lignin to PMMA is 5By means of SnO 2 Has a reduced electron and ion transmission impedance of 0.5 A.g -1 The specific capacitance under the current reaches 406 F.g -1 . However, the electrostatic spinning method has complex operation process, needs to add conductive polymers such as PVP and the like as spinning aids, and has high cost. Xi et al (Industrial Crops)&Products,2021,161, 113179) takes enzymatic hydrolysis lignin as a raw material, and prepares lignin porous carbon with three different microstructures (high graphitization degree, high microporosity and hierarchical porous structure) by regulating and controlling different activating agents through an activation method, and takes the lignin porous carbon as a carbon skeleton and loads nano SnO through ball milling 2 Researches show that the graded porous carbon with larger specific surface area and high mesoporous rate is most beneficial to SnO 2 At a load of 0.1A · g -1 The capacity of the lower circulation of 100 circles reaches 620mAh g -1 . Both documents show that: the lignin porous carbon with proper specific surface area and hierarchical porous structure is favorable for SnO 2 The load of (2).
In view of the foregoing, current references to lignin-based porous charcoals and SnO 2 The research of the compound is less, the electrostatic spinning method reported in the literature has complex process operation and high cost, and the lignin porous carbon/SnO prepared by the ball milling method 2 The compound cannot fundamentally solve SnO 2 The volume expansion effect when applied to the lithium ion battery cathode material and the rapid reduction of the capacity after long-term circulation. Analog graphene/SnO 2 High performance lithium battery negative electrode prepared by reacting SnO 2 The load on the lignin graphene carbon nano-sheets is an effective way for improving the cycle and rate capability of the lignin graphene carbon nano-sheets. The lignin-based porous carbon nanosheets prepared by the existing freezing casting method and template method generally have lower specific surface area and high microporosity, need strong corrosive reagents such as KOH for secondary activation and are not suitable for being used as load SnO 2 The carbon skeleton of (2). The self-assembly method requires control of very low lignin concentration and consumption of large amounts of organic solvents.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention mainly aims to provide a preparation method of a lignin-based graphene porous carbon nanosheet tin dioxide composite material.
The inventionThe method is completed by two steps: taking water-soluble sulfonated lignin as a carbon precursor and a dispersing agent, taking basic magnesium carbonate as a template agent and an activating agent, taking water as a solvent, carrying out self-assembly under heating and stirring to obtain a uniformly dispersed compound, and then carrying out carbonization and acid washing to obtain a lignin type graphene porous carbon nanosheet which is regular in structure, rich in oxygen-containing functional groups (hydroxyl and carboxyl) and hierarchical in porous structure; reacting lignin porous carbon nanosheets as carbon skeletons with stannous salt under hydrothermal condition to obtain nano SnO 2 Growing the composite on the pore canal and the surface of the lignin porous carbon nano sheet in situ.
In the preparation process of the method, the amphipathy of the sulfonated lignin is favorable for the dispersion of the basic magnesium carbonate in water, the sulfonated lignin and the hydroxyl on the surface of the basic magnesium carbonate are self-assembled under the action of hydrogen bonds under the condition of heating and stirring, so that the sulfonated lignin with a three-dimensional network structure is uniformly coated on the surface of the two-dimensional basic magnesium carbonate, and water vapor and CO generated by the decomposition of the basic magnesium carbonate in the carbonization process 2 Protecting oxygen-containing functional groups on the surface of the sulfonated lignin, and decomposing basic magnesium carbonate to generate CO 2 The lignin-based graphene porous carbon nanosheet is regular in structure, rich in oxygen-containing functional groups and hierarchical in porous structure and is obtained through acid washing under the action of gas phase stripping and an in-situ template of MgO. Sn under hydrothermal conditions 2+ Hydrolysis occurs to produce Sn (OH) 4 2- ，Sn(OH) 4 2- Closely combined with hydroxyl and carboxyl on the surface of the lignin graphene porous carbon nano sheet through hydrogen bond action and complexation, sn (OH) 4 2- Further oxidation and dehydration to form nano SnO 2 So that the nano SnO generated in situ 2 Anchored on the porous carbon nano-sheet, and in addition, the porous carbon nano-sheet has a channel structure opposite to SnO 2 Generating a structural confinement effect to enable SnO formed in the pore channel 2 And the nano-chips are embedded on the nano-chips.
The invention also aims to provide the lignin graphene porous carbon nanosheet tin dioxide composite material prepared by the method, wherein SnO 2 The nano particles are uniformly dispersed and tightly anchored on the carbon nano-chip, thereby solving the problem ofSnO 2 The lithium ion battery cathode material has the problems of serious volume expansion and poor conductivity, and improves the specific capacity, the first coulombic efficiency and the rate capability of the lithium ion battery.
In the invention, the lignin-based graphene porous carbon nanosheet SnO 2 SnO in composite materials 2 The particle size of the (B) is 5-10 nm, and the content is not less than 60%.
The invention further aims to provide application of the lignin-based graphene porous carbon nanosheet tin dioxide composite material in a lithium ion battery cathode material.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a lignin-based graphene porous carbon nanosheet tin dioxide composite material comprises the following steps:
(1) Dissolving the sulfonated lignin in water to prepare a solution with the mass concentration of 10-60 mg/ml, wherein the mass ratio of the sulfonated lignin to the basic magnesium carbonate is 1: (1-3) adding basic magnesium carbonate, stirring for 10-30 min at 70-90 ℃, drying, carbonizing for 0.5-5 h at 550-750 ℃, and acid washing to obtain lignin graphene porous carbon nanosheets;
(2) Dispersing lignin graphene porous carbon nano sheets in water to obtain a dispersion liquid with the mass concentration of 1-3 mg/ml, adding a stannous salt dilute acid solution into the dispersion liquid at the speed of 2-10 ml/min, adjusting the pH of the system to 0.5-2.0, stirring at 25-35 ℃ for 0.5-3 h, carrying out hydrothermal reaction at 160-200 ℃ for 6-18 h, cooling, filtering, washing and drying to obtain the lignin graphene porous carbon nano sheets SnO 2 And (3) a compound.
Preferably, the sulfonated lignin of step (1) may be selected from: at least one of sodium lignosulfonate and calcium lignosulfonate in the acid pulping red liquor, sulfonated product of alkali lignin in the alkaline pulping black liquor and sulfonated product of enzymatic lignin in the biorefinery industrial process.
Preferably, the mass concentration of the sulfonated lignin dissolved in the water in the step (1) is 20-40 mg/ml.
Preferably, the mass ratio of the sulfonated lignin to the basic magnesium carbonate in the step (1) is 1:2.
preferably, the stirring temperature in the step (1) is 80 ℃, and the stirring time is 20min.
Preferably, the drying manner in step (1) is at least one of forced air drying, vacuum drying, infrared drying and freeze drying, and more preferably freeze drying.
Preferably, before carbonizing at 550-750 ℃ for 0.5-5 h in step (1), carbonizing at 150-350 ℃ for 10-60 min.
Preferably, the carbonization procedure in step (1) is as follows: heating to 150-350 deg.c at 10 deg.c/min for 10-60 min; then the temperature is raised to 550-750 ℃ at the speed of 5-15 ℃/min, the temperature is kept for 0.5-5 h, and the temperature is reduced to the room temperature.
More preferably, the procedure of the carbonization is as follows: heating to 250 deg.c at 10 deg.c/min for 30-40 min; then the temperature is raised to 650 ℃ at the speed of 10 ℃/min, kept for 2 to 3 hours and then cooled to the room temperature.
Preferably, the carbonization in the step (1) is performed in an inert gas or nitrogen atmosphere, and the inert gas is at least one of argon and helium.
Preferably, the acid washing in the step (1) refers to washing the carbonized product in 0.5-2 mol/L acid solution for 1-3 h, then washing, filtering and drying, wherein the acid solution is hydrochloric acid or sulfuric acid, and the drying may be at least one of forced air drying, vacuum drying, infrared drying and freeze drying.
Preferably, the dilute acid solution of stannous salt in the step (2) is obtained by dissolving stannous salt in 0.05-0.2 mol/L dilute acid, wherein the mass concentration of the stannous salt is 5-15 mg/ml, and more preferably 8-12 mg/ml; the stannous salt is at least one of stannous sulfate, stannous oxalate and stannous chloride, and the dilute acid is one of dilute hydrochloric acid and dilute sulfuric acid.
Preferably, in the step (2), the mass ratio of the lignin-based graphene porous carbon nanosheet to the stannous salt is (2-6): (5-15).
Preferably, the lignin-based graphene porous carbon nanosheet in the step (2) is dispersed in water by ultrasonic for 20-30 min.
Preferably, the pH in step (2) is 0.8 to 1.2.
Preferably, the dilute stannous salt solution in the step (2) is added into the lignin graphene porous carbon nanosheet dispersion at a speed of 2-6 ml/min.
Preferably, the stirring time of the step (2) at 25-35 ℃ is 1-2 h.
Preferably, the temperature of the hydrothermal reaction in the step (2) is 180 ℃, and the hydrothermal time is 12-14 h.
The lignin-based graphene porous carbon nanosheet tin dioxide composite material is prepared by the method.
The lignin-based graphene porous carbon nanosheet tin dioxide composite material is applied to a lithium ion battery cathode material.
The present invention will be described in more detail below.
(1) Dissolving the sulfonated lignin in water to prepare a solution with the mass concentration of 10-60 mg/ml, wherein the mass ratio of the sulfonated lignin to the basic magnesium carbonate is 1: (1-3) adding basic magnesium carbonate, stirring for 10-30 min at 70-90 ℃, drying, carbonizing for 0.5-5 h at 550-750 ℃, and acid washing to obtain lignin graphene carbon nanosheets;
the step is to obtain the lignin graphene carbon nanosheet which is regular in morphology, high in oxygen-containing functional group content and hierarchical porous in structure.
In the step, the basic magnesium carbonate is not only a template agent but also a fire retardant, and the basic magnesium carbonate is decomposed to generate MgO and CO in the subsequent high-temperature carbonization process 2 And water vapor, wherein MgO plays a role of a template agent and can be used for acid washing and pore forming, and on the other hand, mgO forms a barrier to protect hydroxyl and carboxyl oxygen-containing functional groups of lignin in the lignin carbonization process; in addition, CO is formed 2 And water vapor can produce local temperature reduction effect to reduce the decomposition of oxygen-containing functional groups.
In the step, the amphipathy of the sulfonated lignin is utilized to disperse the basic magnesium carbonate powder to obtain a uniformly dispersed dispersion liquid, the concentration of the sulfonated lignin is 10-60 mg/ml, and if the concentration of the sulfonated lignin is lower than 10mg/ml, the subsequent yield of the lignin/basic magnesium carbonate compound is low; if the concentration of the dispersion liquid is higher than 60mg/ml, the lignin and the basic magnesium carbonate are easy to agglomerate by themselves.
In the step, the mass ratio of the sulfonated lignin to the basic magnesium carbonate is 1: (1-3), if the mass ratio of the basic magnesium carbonate is lower than 1, the content of the basic magnesium carbonate in the template agent is too low, so that the prepared lignin-based graphene porous carbon nanosheet is irregular in shape and has fewer pore channels; the carbonization effect of the subsequent product is poor, and the prepared lignin-based graphene porous carbon nanosheet is irregular in shape and less in pore canal; if the mass ratio of the basic magnesium carbonate is higher than 3, the dispersion effect of the sulfonated lignin is influenced, the lignin-based graphene porous carbon nanosheet with irregular shape is obtained, and SnO is not facilitated 2 The load of (2).
In the step, stirring is carried out for 10-30 min at 70-90 ℃ in order to realize hydrogen bond self-assembly of the sulfonated lignin and the basic magnesium carbonate through hydroxyl groups to obtain a compound in which the sulfonated lignin is uniformly attached to the basic magnesium carbonate, wherein the temperature is lower than 70 ℃, the exposed hydroxyl groups on the surface of the basic magnesium carbonate are reduced, the assembly effect with the sulfonated lignin is poor, the exposed hydroxyl groups of the basic magnesium carbonate are reduced, and the assembly effect is poor; the temperature is higher than 90 ℃, so that the moisture is quickly evaporated, the assembly effect of lignin and basic magnesium carbonate is poor, and the formation of the lignin-based graphene carbon nanosheets with regular shapes is not facilitated.
In the step, carbonization is carried out in an inert atmosphere, carbonization is carried out for 0.5-5 h at 550-750 ℃, if the carbonization temperature is too low and the time is too short, carbonization of lignin is incomplete, so that the electronic conductivity of the lignin serving as a conductive carbon skeleton is reduced; if the temperature is too high and the time is too long, the oxygen-containing functional groups on the surfaces of the carbon nano-sheets are completely decomposed, which is not beneficial to SnO 2 While also increasing production costs.
In the step, the carbonized product is washed for 1-3 h in 0.5-2 mol/L acid solution by acid washing, so as to remove MgO generated in situ by decomposition of basic magnesium carbonate in the carbonization process, and obtain the lignin-based graphene porous carbon nanosheet.
(2) Ultrasonically dispersing the carbon nano sheet obtained in the step (1) in water to obtain 100ml of dispersion liquid A with the mass concentration of 1-3 mg/ml, dissolving a certain amount of stannous salt in 0.05-0.2 mol/L diluted acid to obtain 50ml of solution B with the mass concentration of 5-15 mg/ml, slowly dropwise adding the solution B into the solution A, adjusting the pH value to 0.5-2.0, and stirring for 0.5-3 h at the temperature of 25-35 ℃;
the step is to obtain nano SnO 2 The composite material grows in situ on the pore canal, hydroxyl and carboxyl oxygen-containing functional groups of the lignin graphene porous carbon nano sheet.
In the step, the concentration of the carbon nano-sheets is 1-5 mg/ml, and if the concentration is lower than 1mg/ml, the SnO of the carbon nano-sheets 2 The yield of the compound is too low, if the concentration is higher than 5mg/ml, the agglomeration of the carbon nano-sheets is serious, and the nano-SnO is not facilitated 2 Uniform growth of the seed crystal.
In the step, B is slowly dripped into A and stirred for 0.5 to 3 hours at normal temperature so as to lead Sn 2+ Is bonded on the hydroxyl and carboxyl oxygen-containing functional groups of the lignin graphene carbon nano-sheet through electrostatic adsorption and chemical bonds to ensure that Sn 2+ Are uniformly distributed on the carbon nano-chip.
In this step, the stannous salt is dissolved in dilute acid to suppress Sn 2+ In the step of hydrolyzing under stirring at the temperature of between 25 and 35 ℃, the pH is regulated and controlled to realize SnO in the hydrothermal process in the step (3) 2 Particle size control and SnO 2 The key of uniform growth on the carbon nano-chip is that if the pH is lower than 0.5, sn is generated 2+ The hydrolysis rate is too slow in the hydrothermal process, so that SnO in the compound 2 Too low a yield of (a); sn if the pH is higher than 2 2+ The rate of hydrolysis is too fast in the hydrothermal process, resulting in SnO 2 The particles are too large and agglomeration is severe.
(3) Carrying out hydrothermal reaction on the AB mixed solution uniformly mixed in the step (2) at 160-200 ℃ for 6-18 h, cooling to room temperature, filtering and separating, taking filter residue, washing and drying to obtain the lignin graphene porous carbon nanosheet SnO 2 And (c) a complex.
The step is to realize Sn through hydrothermal reaction 2+ Slowly hydrolyzing to obtain in-situ generated nano SnO 2 SnO with strong bonding force with carbon nanosheets 2 Lignin-based graphene porous carbon nanosheet with good crystal structureSnO 2 A composite material.
The step controls the hydrothermal temperature at 160 ℃, the hydrothermal time at 6-18 h, the time is too long, and the temperature is too high, so that the formed SnO 2 Larger grains, resulting in SnO 2 Agglomeration and increased production cost; when the time is too short and the temperature is too low, the resultant SnO 2 The crystal form of (A) is poor, and the yield of the compound is low.
The invention provides a method for preparing lignin graphene porous carbon nanosheet SnO by using the method 2 The specific surface area of the composite material and the porous carbon is 1089m 2 ·g -1 The specific surface area of the composite is 150-300m 2 ·g -1 SnO in the composite 2 The particle size of the (B) is 5-10 nm, and the content is not less than 60%. Can be applied to the field of lithium ion battery cathode materials.
The method is favorable for dispersing basic magnesium carbonate in water based on amphipathy of the sulfonated lignin, and hydroxyl on the surfaces of the sulfonated lignin and the basic magnesium carbonate are self-assembled under the action of hydrogen bonds under the condition of heating and stirring, so that the sulfonated lignin with a three-dimensional network structure is uniformly coated on the surface of two-dimensional basic magnesium carbonate, on one hand, the basic magnesium carbonate is used as a flame retardant, and MgO, water vapor and CO generated by decomposition of the basic magnesium carbonate in the carbonization process 2 Protecting oxygen-containing functional groups on the surface of the sulfonated lignin, and decomposing generated CO by using basic magnesium carbonate as a template agent 2 And MgO, and the lignin graphene porous carbon nanosheet has the effects of gas phase stripping and in-situ template function, and is regular in structure, rich in oxygen-containing functional groups and hierarchical porous structure. Sn under hydrothermal conditions 2+ Hydrolysis occurs to produce Sn (OH) 4 2- ，Sn(OH) 4 2- Closely combined with hydroxyl and carboxyl on the surface of the lignin graphene porous carbon nano sheet through hydrogen bonding and complexing, sn (OH) 4 2- Further oxidation and dehydration to form nano SnO 2 So that the nano SnO generated in situ 2 Anchored on the porous carbon nano-sheet, and in addition, the porous carbon nano-sheet has a channel structure opposite to SnO 2 Generating the function of structural confinement so as to form SnO in the pore canal 2 And is embedded on the nano-chip.The two-dimensional composite material reserves partial pore channel structure, has larger specific surface area, and is beneficial to the contact of the composite material and electrolyte and Li + Nano SnO 2 Combined in the surface and in the channels, shortening Li + The transmission distance greatly improves the reversible capacity, the cycle performance and the rate capability of the composite material.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The lignin graphene porous carbon nanosheet SnO prepared by the invention 2 The composite material has regular two-dimensional sheet shape and ordered structure, and is used as nano SnO of a main active substance 2 The two-dimensional graphene-like porous carbon nanosheets can improve the overall electronic diffusion rate of the composite material and effectively inhibit nano SnO 2 The volume effect brought by the charge and discharge process, and the two-dimensional porous structure greatly shortens Li + The transmission distance is higher in reversible capacity, excellent in cycle performance and rate capability when applied to the negative electrode of the lithium ion battery.
(2) The lignin graphene porous carbon nanosheet SnO provided by the invention 2 In the preparation process of the composite material, water-soluble sulfonated lignin is used as a carbon precursor and a dispersing agent, weak-corrosive basic magnesium carbonate is used as a template agent, and stannous salt is used as a tin source, so that the nano SnO is realized 2 The lignin-based graphene porous carbon nanosheet is uniformly loaded and tightly anchored, the raw material source is wide, the price is low, the raw material source is easy to obtain, the preparation process is simple, green and environment-friendly, the high added value utilization of lignin is realized, and the environment protection is facilitated.
Drawings
Fig. 1 is a scanning electron microscope image of a lignin-based graphene porous carbon nanosheet prepared in example 1 of the present invention.
Fig. 2 is a transmission electron microscope image of the lignin-based graphene porous carbon nanosheet prepared in example 1 of the present invention.
FIG. 3 shows a lignin-based graphene porous carbon nanosheet SnO prepared in embodiment 1 of the invention 2 Scanning electron micrograph of composite。
FIG. 4 shows a lignin-based graphene porous carbon nanosheet SnO prepared in embodiment 1 of the invention 2 Transmission electron microscopy of the composite.
Fig. 5 is a raman spectrum of the lignin-based graphene porous carbon nanosheet prepared in example 1 of the present invention.
FIG. 6 shows lignin-based graphene porous carbon nanosheets and lignin-based graphene porous nanosheets SnO prepared in embodiment 1 of the present invention 2 The nitrogen adsorption and desorption curve chart of the composite material.
FIG. 7 shows lignin-based graphene porous carbon nanosheets and lignin-based graphene porous nanosheets SnO prepared in example 1 of the present invention 2 Pore size distribution profile of the composite.
FIG. 8 shows that the lignin-based graphene porous carbon nanosheet SnO prepared in embodiment 1 of the invention 2 Cycle performance profile of the composite.
Fig. 9 shows a lignin-based graphene porous carbon nanosheet SnO prepared in embodiment 1 of the present invention 2 Graph of rate capability of composite material.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The examples of the present invention, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Example 1
Dissolving 2.5g of sodium lignosulfonate in 100ml of deionized water, adding 5g of basic magnesium carbonate into the lignin dispersion according to the mass ratio of 1; grinding the dried product into powder, carbonizing in nitrogen atmosphere, heating to 250 deg.C at 10 deg.C/min, maintaining for 30min, heating to 650 deg.C at 10 deg.C/min, maintaining for 3h, and cooling to room temperature; and soaking the carbonized product in 1mol/L hydrochloric acid for washing for 2h, then washing with water, filtering, and vacuum-drying at 80 ℃ for 12h to obtain the lignin-based graphene porous carbon nanosheet.
Dispersing 0.2g of lignin graphene porous carbon nanosheets in 100ml of water, performing ultrasonic treatment for 30min to obtain a dispersion liquid A, dissolving 0.50g of stannous chloride in 50ml of 0.1mol/L diluted hydrochloric acid to obtain a solution B, dropwise adding the solution B into the solution A at a speed of 4ml/min by using a peristaltic pump, adjusting the pH value to 1.0 by using 0.1mol/L diluted hydrochloric acid, and stirring for 2h at 28 ℃.
Carrying out hydrothermal reaction on the AB mixed solution at 180 ℃ for 12h, cooling to room temperature, filtering and separating, taking filter residue, washing with water, and carrying out vacuum drying at 80 ℃ for 12h to obtain lignin type graphene porous carbon nanosheet SnO 2 A composite material.
Example 2
Dissolving 1.5g of calcium lignosulphonate in 100ml of deionized water, adding 4.5g of basic magnesium carbonate into lignin dispersion according to the mass ratio of 1; grinding the dried product into powder, carbonizing in argon atmosphere, heating to 300 ℃ at a speed of 10 ℃/min, preserving heat for 20min, heating to 550 ℃ at a speed of 5 ℃/min, preserving heat for 5h, and cooling to room temperature; and (3) soaking the carbonized product in 2mol/L sulfuric acid, washing for 30min, then washing with water, filtering, and carrying out infrared drying at 80 ℃ for 12h to obtain the lignin-based graphene porous carbon nanosheet.
0.2g of lignin graphene porous carbon nanosheet is dispersed in 100ml of water, ultrasonic treatment is carried out for 30min to obtain a dispersion liquid A, 0.57g of stannous sulfate is dissolved in 50ml of 0.05mol/L dilute sulfuric acid to obtain a solution B, the solution B is dripped into the solution A at the speed of 3ml/min by using a peristaltic pump, the pH value is adjusted to 1.5 by using 0.05mol/L dilute sulfuric acid, and the solution B is stirred for 3h at the temperature of 30 ℃.
Carrying out hydrothermal reaction on the AB mixed solution at 160 ℃ for 16h, cooling to room temperature, filtering and separating, taking filter residue, washing with water, and carrying out infrared drying at 80 ℃ for 12h to obtain the lignin-based graphene porous carbon nanosheet SnO 2 A composite material.
Example 3
Dissolving 5g of sulfonated alkali lignin in 100ml of deionized water, adding 5g of basic magnesium carbonate into the lignin dispersion according to the mass ratio of the sulfonated alkali lignin to the basic magnesium carbonate of 1; grinding the dried product into powder, carbonizing in helium atmosphere, heating to 200 deg.C at 10 deg.C/min, maintaining for 50min, heating to 750 deg.C at 15 deg.C/min, maintaining for 1h, and cooling to room temperature; and soaking the carbonized product in 0.5mol/L hydrochloric acid, washing for 2h, then washing with water, filtering, and vacuum drying at 80 ℃ for 12h to obtain the lignin-based graphene porous carbon nanosheet.
0.3g of lignin graphene porous carbon nanosheet is dispersed in 100ml of water, ultrasonic treatment is carried out for 25min to obtain a dispersion liquid A, 0.75g of stannous oxalate is dissolved in 50ml of 0.2mol/L diluted hydrochloric acid to obtain a solution B, the solution B is dripped into the solution A at the speed of 6ml/min by using a peristaltic pump, the pH value is adjusted to 0.5 by using 0.2mol/L diluted hydrochloric acid, and the solution is stirred for 1.5h at the temperature of 25 ℃.
Carrying out hydrothermal reaction on the AB mixed solution at 200 ℃ for 6h, cooling to room temperature, filtering and separating, taking filter residue, washing with water, and carrying out vacuum drying at 80 ℃ for 12h to obtain lignin type graphene porous carbon nanosheet SnO 2 A composite material.
Example 4
Dissolving 3g of sulfonated enzymatic hydrolysis lignin in 100ml of deionized water, adding 6g of basic magnesium carbonate into the lignin dispersion according to the mass ratio of the sulfonated lignin to the basic magnesium carbonate of 1; grinding the dried product into powder, carbonizing in nitrogen atmosphere, heating to 150 deg.C at 10 deg.C/min, maintaining for 60min, heating to 650 deg.C at 15 deg.C/min, maintaining for 2h, and cooling to room temperature; and (3) soaking the carbonized product in 0.5mol/L sulfuric acid, washing for 2h, then washing with water, filtering, and carrying out infrared drying at 80 ℃ for 12h to obtain the lignin graphene porous carbon nanosheet.
0.1g of lignin graphene porous carbon nanosheet is dispersed in 100ml of water, ultrasonic treatment is carried out for 20min to obtain a dispersion liquid A, 0.25g of stannous oxalate is dissolved in 50ml of 0.05mol/L dilute sulfuric acid to obtain a solution B, the solution B is dripped into the solution A at the speed of 2ml/min by using a peristaltic pump, the pH value is adjusted to 2.0 by using 0.05mol/L dilute sulfuric acid, and the solution B is stirred for 1h at the temperature of 32 ℃.
Carrying out hydrothermal reaction on the AB mixed solution at 170 ℃ for 18h, cooling to room temperature, filtering and separating, taking filter residue, washing with water, and carrying out infrared drying at 80 ℃ for 12h to obtain the lignin-based graphene porous carbon nanosheet SnO 2 A composite material.
Example 5
Dissolving 1g of sodium lignosulfonate in 100ml of deionized water, adding 3g of basic magnesium carbonate into the lignin dispersion according to the mass ratio of 1; grinding the dried product into powder, carbonizing in argon atmosphere, heating to 250 deg.C at 10 deg.C/min, maintaining for 40min, heating to 550 deg.C at 5 deg.C/min, maintaining for 3h, and cooling to room temperature; and soaking the carbonized product in 2mol/L sulfuric acid, washing for 1h, then washing with water, filtering, and carrying out infrared drying at 80 ℃ for 12h to obtain the lignin-based graphene porous carbon nanosheet.
Dispersing 0.1g of lignin graphene porous carbon nanosheets in 100ml of water, performing ultrasonic treatment for 20min to obtain a dispersion liquid A, dissolving 0.29g of stannous sulfate in 50ml of 0.1mol/L dilute sulfuric acid to obtain a solution B, dropwise adding the solution B into the solution A at a speed of 4ml/min by using a peristaltic pump, adjusting the pH value to 1.2 by using 0.1mol/L dilute sulfuric acid, and stirring for 3h at 35 ℃.
Carrying out hydrothermal reaction on the AB mixed solution at 190 ℃ for 10h, cooling to room temperature, filtering and separating, taking filter residue, washing with water, and carrying out infrared drying at 80 ℃ for 12h to obtain the lignin-based graphene porous carbon nanosheet SnO 2 A composite material.
Example 6
Dissolving 6g of sulfonated enzymatic hydrolysis lignin in 100ml of deionized water, adding 6g of basic magnesium carbonate into the lignin dispersion according to the mass ratio of the sulfonated lignin to the basic magnesium carbonate of 1; grinding the dried product into powder, carbonizing in helium atmosphere, heating to 350 deg.C at 10 deg.C/min, maintaining for 10min, heating to 750 deg.C at 10 deg.C/min, maintaining for 30min, and cooling to room temperature; and soaking the carbonized product in 1mol/L hydrochloric acid, washing for 1h, then washing with water, filtering, and drying in vacuum at 80 ℃ for 12h to obtain the lignin-based graphene porous carbon nanosheet.
0.3g of lignin graphene porous carbon nanosheet is dispersed in 100ml of water, ultrasonic treatment is carried out for 25min to obtain a dispersion liquid A, 0.70g of stannous chloride is dissolved in 50ml of 0.15mol/L diluted hydrochloric acid to obtain a solution B, the solution B is dripped into the solution A by using a peristaltic pump at the speed of 10ml/min, the pH value is adjusted to 0.8 by using 0.15mol/L diluted hydrochloric acid, and the solution B is stirred for 30min at the temperature of 30 ℃.
Carrying out hydrothermal reaction on the AB mixed solution at 180 ℃ for 12h, cooling to room temperature, filtering and separating, taking filter residue, washing with water, and carrying out vacuum drying at 80 ℃ for 12h to obtain lignin type graphene porous carbon nanosheet SnO 2 A composite material.
Description of the effects of the embodiments
The lignin-based graphene porous carbon nanosheets and the lignin-based graphene porous carbon nanosheets SnO prepared in example 1 2 The composite material was subjected to material characterization, and the results are shown in FIGS. 1 to 6; para-lignin graphene porous carbon nanosheet SnO 2 The composite material is applied to the lithium ion battery cathode material for electrochemical test, and the results are shown in figures 7-8 and table 1.
The morphology and size of the samples of the invention were characterized by a field emission scanning electron microscope (SEM, hitachi S-550) and a high-resolution field emission transmission electron microscope (HRTEM, JEM-2100F, 200kv). The specific surface area and channel structure of the samples were tested using a fully automated specific surface and porosity analyzer (Micromeritics ASAP 2020 instrument). The degree of graphitization of the sample was tested using a raman spectrometer (LabRAM HR Evolution).
The battery assembly adopts half battery assembly, and the model is CR2032. The positive electrode material comprises 80wt% of active substance, 10wt% of carbon black and 10wt% of polyvinylidene fluoride (PVDF), and is coated by taking N-methyl-2-pyrrolidone (NMP) as a solvent, wherein the active substance is the lignin graphene porous carbon nanosheet SnO prepared by the method 2 A composite material. The lithium sheet is used as a counter electrode, and the electrolyte is 1mol/L LiPF 6 As solute, the volume ratio of 1:1:1 Ethylene Carbonate (EC), ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) as solvent. The whole installation process of the lithium ion half cell is finished in an argon-protected glove box. The constant current charging/discharging performance test of the battery is carried out by using a Neware battery performance test system in a voltage range of 0.01V-3.0V and at a current density of 200mA/g, and the multiplying power performance test is completed at current densities of 50mA/g, 100mA/g, 200mA/g, 500mA/g and 1000 mA/g.
TABLE 1 isThe lignin-based graphene porous carbon nanosheet SnO prepared in the above embodiment 2 Comparison of the nanocomposite with the samples prepared in the comparative examples described below in terms of cycle performance.
The preparation process of the comparative example was as follows:
comparative example 1 (pure SnO 2 )
0.5g of stannous chloride was dissolved in 150ml of 0.1mol/L dilute hydrochloric acid, the pH was adjusted to 1 with 0.1mol/L dilute hydrochloric acid, and the mixture was stirred at 28 ℃ for 2 hours. Carrying out hydrothermal reaction on a stannous chloride solution at 180 ℃ for 12h, cooling to room temperature, filtering and separating, taking filter residue, washing with water, and carrying out vacuum drying at 80 ℃ for 12h to obtain pure nano SnO 2 。
Comparative example 2 (pure lignin graphene porous carbon nanosheet)
Dissolving 2.5g of sodium lignosulfonate in 100ml of deionized water, adding 5g of basic magnesium carbonate into the lignin dispersion according to the mass ratio of 1; grinding the dried product into powder, carbonizing in nitrogen atmosphere, heating to 250 deg.C at 10 deg.C/min, maintaining for 30min, heating to 650 deg.C at 10 deg.C/min, maintaining for 3h, and cooling to room temperature; and soaking the carbonized product in 1mol/L hydrochloric acid for washing for 2h, then washing with water, filtering, and vacuum-drying at 80 ℃ for 12h to obtain the lignin-based graphene porous carbon nanosheet.
Comparative example 3 (non-sulfonated alkali lignin as raw material)
Dispersing 2.5g of unsulfonated alkali lignin in 100ml of deionized water, adding 5g of basic magnesium carbonate into the lignin dispersion according to the mass ratio of the alkali lignin to the basic magnesium carbonate of 1; grinding the dried product into powder, carbonizing in nitrogen atmosphere, heating to 250 deg.C at 10 deg.C/min, maintaining for 30min, heating to 650 deg.C at 10 deg.C/min, maintaining for 3h, and cooling to room temperature; and soaking the carbonized product in 1mol/L hydrochloric acid for washing for 2h, then washing with water, filtering, and vacuum-drying at 80 ℃ for 12h to obtain the lignin-based graphene porous carbon nanosheet.
0.2g of lignin graphene porous carbon nanosheet is dispersed in 100ml of water, ultrasonic treatment is carried out for 30min to obtain a dispersion liquid A, 0.50g of stannous chloride is dissolved in 50ml of 0.1mol/L diluted hydrochloric acid to obtain a solution B, the solution B is dripped into the solution A by a peristaltic pump at the speed of 4ml/min, the pH value is adjusted to 1.0 by 0.1mol/L diluted hydrochloric acid, and stirring is carried out for 2h at the temperature of 28 ℃.
Carrying out hydrothermal reaction on the AB mixed solution at 180 ℃ for 12h, cooling to room temperature, filtering and separating, taking filter residue, washing with water, and vacuum drying at 80 ℃ for 12h to obtain the lignin-based graphene porous carbon nanosheet SnO 2 A composite material.
Comparative example 4 (raw material of non-sulfonated enzymatic hydrolysis lignin)
Dispersing 2.5g of non-sulfonated enzymatic hydrolysis lignin in 100ml of deionized water, adding 5g of basic magnesium carbonate into the lignin dispersion according to the mass ratio of the enzymatic hydrolysis lignin to the basic magnesium carbonate of 1; grinding the dried product into powder, carbonizing in nitrogen atmosphere, heating to 250 deg.C at 10 deg.C/min, maintaining for 30min, heating to 650 deg.C at 10 deg.C/min, maintaining for 3h, and cooling to room temperature; and (3) soaking the carbonized product in 1mol/L hydrochloric acid, washing for 2h, then washing with water, filtering, and vacuum drying at 80 ℃ for 12h to obtain the lignin graphene porous carbon nanosheet.
0.2g of lignin graphene porous carbon nanosheet is dispersed in 100ml of water, ultrasonic treatment is carried out for 30min to obtain a dispersion liquid A, 0.50g of stannous chloride is dissolved in 50ml of 0.1mol/L diluted hydrochloric acid to obtain a solution B, the solution B is dripped into the solution A by a peristaltic pump at the speed of 4ml/min, the pH value is adjusted to 1.0 by 0.1mol/L diluted hydrochloric acid, and stirring is carried out for 2h at the temperature of 28 ℃.
Carrying out hydrothermal reaction on the AB mixed solution at 180 ℃ for 12h, cooling to room temperature, filtering and separating, taking filter residue, washing with water, and vacuum drying at 80 ℃ for 12h to obtain the lignin-based graphene porous carbon nanosheet SnO 2 A composite material.
Comparative example 5 (No hydrothermal Process, direct filtration after agitation)
Dissolving 2.5g of sodium lignosulfonate in 100ml of deionized water, adding 5g of basic magnesium carbonate into the lignin dispersion according to the mass ratio of 1; grinding the dried product into powder, carbonizing in nitrogen atmosphere, heating to 250 deg.C at 10 deg.C/min, maintaining for 30min, heating to 650 deg.C at 10 deg.C/min, maintaining for 3h, and cooling to room temperature; and (3) soaking the carbonized product in 1mol/L hydrochloric acid, washing for 2h, then washing with water, filtering, and vacuum drying at 80 ℃ for 12h to obtain the lignin graphene porous carbon nanosheet.
Dispersing 0.2g of lignin graphene porous carbon nanosheet in 100ml of water, performing ultrasonic treatment for 30min to obtain a dispersion liquid A, dissolving 0.50g of stannous chloride in 50ml of 0.1mol/L diluted hydrochloric acid to obtain a solution B, dropwise adding the solution B into the solution A at the speed of 4ml/min by using a peristaltic pump, adjusting the pH to 1.0 by using 0.1mol/L diluted hydrochloric acid, stirring for 2h at 28 ℃, filtering and separating, taking filter residue, washing with water, and performing vacuum drying for 12h at 80 ℃ to obtain the lignin graphene porous carbon nanosheet (SnO) (SnO 2 Negligible yield).
Comparative example 6 (direct carbonization sulfonated Lignin C/SnO 2 )
Grinding 2.5g of sodium lignosulfonate into powder, carbonizing in nitrogen atmosphere, heating to 250 ℃ at a speed of 10 ℃/min, keeping the temperature for 30min, heating to 650 ℃ at a speed of 10 ℃/min, keeping the temperature for 3h, and cooling to room temperature; and soaking the carbonized product in 100ml of 1mol/L hydrochloric acid, washing for 2h, filtering, and vacuum drying at 80 ℃ for 12h to obtain the directly carbonized sulfonated lignin carbon.
Dispersing 0.2g of direct carbonized sulfonated lignin carbon in 100ml of water, performing ultrasonic treatment for 30min to obtain a dispersion liquid A, dissolving 0.50g of stannous chloride in 50ml of 0.1mol/L diluted hydrochloric acid to obtain a solution B, dropwise adding the solution B into the solution A at the speed of 4ml/min by using a peristaltic pump, adjusting the pH value to 1.0 by using 0.1mol/L diluted hydrochloric acid, and stirring for 2h at 28 ℃.
Carrying out hydrothermal reaction on the AB mixed solution at 180 ℃ for 12h, cooling to room temperature, filtering and separating, taking filter residue, washing with water, and carrying out vacuum drying at 80 ℃ for 12h to obtain the direct carbonized sulfonated lignin carbon SnO 2 A composite material.
Comparative example 7 (KOH-activated Lignin porous charcoal/SnO 2 )
Dissolving 2.5g of sodium lignosulfonate in 100ml of deionized water, adding 5g of KOH into the lignin dispersion according to the mass ratio of 1; grinding the dried product into powder, carbonizing in nitrogen atmosphere, heating to 250 deg.C at 10 deg.C/min, maintaining for 30min, heating to 650 deg.C at 10 deg.C/min, maintaining for 3h, and cooling to room temperature; and soaking the carbonized product in 1mol/L hydrochloric acid for washing for 2h, then washing with water, filtering, and carrying out vacuum drying at 80 ℃ for 12h to obtain the KOH activated lignin porous carbon.
Dispersing 0.2g of KOH activated lignin porous carbon in 100ml of water, performing ultrasonic treatment for 30min to obtain a dispersion liquid A, dissolving 0.50g of stannous chloride in 50ml of 0.1mol/L diluted hydrochloric acid to obtain a solution B, dropwise adding the solution B into the solution A at the speed of 4ml/min by using a peristaltic pump, adjusting the pH value to 1.0 by using 0.1mol/L diluted hydrochloric acid, and stirring for 2h at 28 ℃.
Carrying out hydrothermal reaction on the AB mixed solution at 180 ℃ for 12h, cooling to room temperature, filtering and separating, taking filter residue, washing with water, and carrying out vacuum drying at 80 ℃ for 12h to obtain KOH activated lignin porous carbon SnO 2 A composite material.
Comparative example 8 (ZnCO) 3 Activated lignin porous carbon/SnO 2 )
2.5g of sodium lignosulfonate is dissolved in 80ml of deionized water, and 5g of ZnCO is taken according to the mass ratio of 1 3 Adding into 20ml deionized water, ultrasonic dispersing for 10min, and adding ZnCO 3 Dropwise adding the dispersion into sodium lignosulfonate solution, stirring at 80 deg.C for 20min, and freeze drying; grinding the dried product into powder, carbonizing in nitrogen atmosphere, heating to 250 deg.C at 10 deg.C/min, maintaining for 30min, heating to 650 deg.C at 10 deg.C/min, maintaining for 3h, and cooling to room temperature; soaking the carbonized product in 1mol/L hydrochloric acid for washing for 2h, then washing with water, filtering, and vacuum drying at 80 ℃ for 12h to obtain ZnCO 3 Activated lignin porous carbon.
0.2g of ZnCO is taken 3 Dispersing activated lignin porous carbon in 100ml of water, performing ultrasonic treatment for 30min to obtain a dispersion liquid A, dissolving 0.50g of stannous chloride in 50ml of 0.1mol/L diluted hydrochloric acid to obtain a solution B, dropwise adding the solution B into the solution A at the speed of 4ml/min by using a peristaltic pump, adjusting the pH value to 1.0 by using 0.1mol/L diluted hydrochloric acid, and stirring for 2h at the temperature of 28 ℃.
Carrying out hydrothermal reaction on the AB mixed solution at 180 ℃ for 12h, cooling to room temperature, filtering and separating, taking filter residue, washing with water, and carrying out vacuum drying at 80 ℃ for 12h to obtain ZnCO 3 Activated lignin porous carbon SnO 2 A composite material.
TABLE 1 Lignin-based graphene porous carbon nanosheet SnO 2 Cycle Performance of composites with comparative examples 1-8
Figure GDA0003398150730000201
Figure GDA0003398150730000211
Table 1 illustrates:
the lignin-based graphene porous carbon nanosheet composite material prepared in example 1 is 200 mA-g -1 The specific discharge capacity after 100 cycles under the current density is 936mAh g -1 And the cycling stability is better, and the cycling performance of all samples of the examples is better than that of other samples of the comparative examples, which is mainly benefited by the nano SnO formed in situ 2 Tightly anchored on the lignin graphene-like carbon nanosheet, volume expansion in the charging and discharging process is limited, the high graphitization degree of the graphene-like carbon nanosheet improves the conductivity of the material, and the nano size of the material shortens Li + The transmission path of (1).
The cycle performance data for the comparative example in Table 1 shows that it is also 200mA g -1 After 100 times of circulation, the pure nano SnO of comparative example 1 2 Because the volume expansion in the charging and discharging process is not effectively inhibited, the specific discharge capacity of the lithium ion battery is only 103mAh g after 100 cycles -1 (ii) a Comparative example 2 since there is no SnO supported 2 The lithium storage capacity is only contributed by the graphene-like carbon nano-sheets, and the capacity is 420mAh g after 100 times of circulation -1 (ii) a Comparative examples 3 and 4 use non-sulfonated lignin as a raw material, and because the non-sulfonated lignin is insoluble in water, the dispersion effect in water is poor, and the assembly effect with basic magnesium carbonate is poor, the generated carbon nanosheet is seriously agglomerated, which is not beneficial to subsequent nano SnO 2 Resulting in 100 cycles of reversible capacity of 417 and 399mAh g respectively -1 The retention rate of the first charge capacity was only 61.7% and 622%, which shows that the sulfonated lignin has a key effect on forming the lignin graphene carbon nanosheets with regular structures; comparative example 5 since there is no hydrothermal process, stannous chloride is hardly hydrolyzed at room temperature and pH =1, and the obtained product is a graphene-like carbon nanosheet, the 100-cycle specific discharge capacity is 435mAh · g -1 The capacity of the graphene-like carbon nanosheet is substantially equal to that of the pure graphene-like carbon nanosheet in comparative example 2, which indicates that the subsequent hydrothermal reaction is an indispensable step; the lignin carbon obtained by directly carbonizing the sulfonated lignin is used as a conductive carbon skeleton, and the lignin carbon is in a micron-level blocky structure due to collapse of a three-dimensional website structure in the carbonization process of the lignin, has low electronic conductivity, lacks a pore structure and surface oxygen-containing functional groups, and cannot effectively anchor nano SnO 2 Causing rapid capacity decay after circulation, the capacity of 100 times of circulation is only 209mAh g -1 (ii) a Comparative examples 7 and 8 with KOH and ZnCO, respectively 3 High-microporosity carbon obtained as activating agent and high-mesoporosity carbon loaded SnO as conductive carbon skeleton 2 Due to KOH and ZnCO during the carbonization process 3 Can not protect oxygen-containing functional groups of lignin to cause SnO 2 The load sites are reduced, and the nano SnO is loaded mainly through a pore channel structure 2 Furthermore, the porous carbon prepared by the two activators is micron-sized, so that Li is enabled + The transmission path of (1) was extended, and these reasons resulted in that the capacity of the materials obtained in comparative examples 4 and 5 was only 501 and 557mAh g -1 。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of a lignin-based graphene porous carbon nanosheet tin dioxide composite material is characterized by comprising the following steps:
(1) Dissolving the sulfonated lignin in water to prepare a solution with the mass concentration of 10-60 mg/ml, wherein the mass ratio of the sulfonated lignin to the basic magnesium carbonate is 1: (1-3) adding basic magnesium carbonate, stirring for 10-30 min at 70-90 ℃, drying, carbonizing for 0.5-5 h at 550-750 ℃, and acid washing to obtain lignin graphene porous carbon nanosheets;
(2) Dispersing lignin graphene porous carbon nano sheets in water to obtain a dispersion liquid with the mass concentration of 1-3 mg/ml, adding a stannous salt dilute acid solution into the dispersion liquid at the speed of 2-10 ml/min, adjusting the pH of the system to 0.5-2.0, stirring at 25-35 ℃ for 0.5-3 h, carrying out hydrothermal reaction at 160-200 ℃ for 6-18 h, cooling, filtering, washing and drying to obtain the lignin graphene porous carbon nano sheets SnO 2 A complex;
the dilute acid solution of the stannous salt in the step (2) is obtained by dissolving stannous salt in 0.05-0.2 mol/L dilute acid.
2. The preparation method of the lignin-based graphene porous carbon nanosheet tin dioxide composite material according to claim 1, wherein in the step (2), the mass ratio of the lignin-based graphene porous carbon nanosheet to the stannous salt is (2-6): (5-15).
3. The preparation method of the lignin-based graphene porous carbon nanosheet tin dioxide composite material according to claim 1, wherein the mass concentration of stannous salt in the dilute stannous salt solution in the step (2) is 5-15 mg/ml; the stannous salt is at least one of stannous sulfate, stannous oxalate and stannous chloride, and the dilute acid is one of dilute hydrochloric acid and dilute sulfuric acid.
4. The preparation method of the lignin-based graphene porous carbon nanosheet tin dioxide composite material according to claim 1, wherein before carbonizing at 550-750 ℃ for 0.5-5 h in step (1), carbonizing at 150-350 ℃ for 10-60 min;
the carbonization procedure in the step (1) is as follows: heating to 150-350 deg.c at 10 deg.c/min for 10-60 min; then raising the temperature to 550-750 ℃ at a speed of 5-15 ℃/min, keeping the temperature for 0.5-5 h, and cooling to room temperature;
and (2) carbonizing in the step (1) under the atmosphere of inert gas or nitrogen, wherein the inert gas is at least one of argon and helium.
5. The preparation method of the lignin-based graphene porous carbon nanosheet tin dioxide composite material according to claim 1, wherein in step (1), the mass concentration of the sulfonated lignin dissolved in water is 20-40 mg/ml; the mass ratio of the sulfonated lignin to the basic magnesium carbonate in the step (1) is 1:2.
6. the preparation method of the lignin-based graphene porous carbon nanosheet tin dioxide composite material according to claim 1, wherein the dilute stannous acid solution in the step (2) is added to the lignin-based graphene porous carbon nanosheet dispersion at a rate of 2-6 ml/min; the pH value in the step (2) is 0.8-1.2.
7. The preparation method of the lignin-based graphene porous carbon nanosheet tin dioxide composite material according to claim 1, wherein the stirring time at 25-35 ℃ in step (2) is 1-2 h; the temperature of the hydrothermal reaction in the step (2) is 180 ℃, and the hydrothermal time is 12-14 h.
8. The preparation method of the lignin-based graphene porous carbon nanosheet tin dioxide composite material according to claim 1, wherein the acid washing in the step (1) is to wash the carbonized product in 0.5-2 mol/L acid solution for 1-3 h, then wash with water, filter and dry, wherein the acid solution is hydrochloric acid or sulfuric acid;
the sulfonated lignin in the step (1) is selected from the following groups: at least one of sodium lignosulfonate in the red liquor of the acid pulping, calcium lignosulfonate in the red liquor of the acid pulping, a sulfonated product of alkali lignin in the black liquor of the alkali pulping, and a sulfonated product of enzymatic lignin in the process of the biorefinery industry.
9. The lignin-based graphene porous carbon nanosheet tin dioxide composite material prepared by the method of any one of claims 1 to 8.
10. The application of the lignin-based graphene porous carbon nanosheet tin dioxide composite material in the negative electrode material of the lithium ion battery according to claim 9.
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