CN117374262B - Endogenous heterojunction anode material, preparation method thereof, negative electrode and lithium ion battery - Google Patents

Endogenous heterojunction anode material, preparation method thereof, negative electrode and lithium ion battery Download PDF

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CN117374262B
CN117374262B CN202311675717.1A CN202311675717A CN117374262B CN 117374262 B CN117374262 B CN 117374262B CN 202311675717 A CN202311675717 A CN 202311675717A CN 117374262 B CN117374262 B CN 117374262B
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fetio
heterojunction
endogenous
anode material
precursor
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CN117374262A (en
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王晓欢
陈洋
原志鹏
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Inner Mongolia University of Technology
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Abstract

The invention discloses an endogenous heterojunction anode material and a preparation method thereof, a negative electrode and a lithium ion battery, wherein the endogenous heterojunction anode material comprises a graphene substrate and FeTiO (FeTiO) adhered on the graphene substrate 3 And Fe (Fe) 2 TiO 5 The multi-layer nano sheet structure of the built-up endogenous heterojunction. The preparation method comprises the following steps: feTiO containing cross-linking agent, graphene oxide and three-dimensional network structure 3 And (3) dropwise adding an alkaline solution into the precursor solution, standing and aging, drying, and then reducing and sintering the dried product. Innovatively utilizes oxygen-containing functional groups and reducing atmosphere in GO to induce phase change through redox synergy, thereby skillfully constructing FeTiO 3 @Fe 2 TiO 5 The built-in battery produced by the internal heterojunction promotes the migration of electron carriers due to the difference of charge distribution of the heterojunction interface, improves the material conductivity, accelerates the lithium storage reaction kinetics, and has excellent electrochemical performance.

Description

Endogenous heterojunction anode material, preparation method thereof, negative electrode and lithium ion battery
Technical Field
The invention relates to the technical field of lithium batteries, in particular to an endogenous heterojunction anode material, a preparation method thereof, a negative electrode and a lithium ion battery.
Background
The advent of lithium-ion batteries (LIBs) breaks through the traditional energy storage mode, and is widely applied to portable electronic equipment, electric automobile energy storage equipment and other aspects. Anode material as key component of lithium ion battery, direct shadowThe research of anode materials has important significance in the application and development of lithium ion batteries in response to the performance of the lithium batteries. The current common commercial graphite anode has low theoretical capacity (372 mAh/g) and seriously affects the development of the lithium ion battery. While other high capacity anode materials (e.g., fe 2 O 3 、Co 3 O 4 、ZnMn 2 O 4 Etc.) have irreversible volume expansion problems, resulting in poor cycling performance, which limit their use in lithium ion batteries.
The transition metal titanate has both embedded and conversion lithium storage modes, has the characteristics of higher energy density, proper discharge potential and good circulation stability, can reduce volume expansion, and is widely focused on anode materials of lithium ion batteries. Ferrous titanate (FeTiO) 3 ) TiO is combined as Transition Metal Titanates (TMTs) 2 And transition metal oxides, and have attracted attention from researchers due to the abundance of resources, environmental friendliness, and low cost. Currently, feTiO is considered to be 3 The electrode has two main lithium intercalation mechanisms. One of which simply intercalates lithium ions, and the second of which is an electrode accompanying a redox conversion reaction during intercalation of lithium, to form or decompose into Li 2 O。FeTiO 3 Has both intercalation and conversion modes of lithium storage, thus Li + Particle breakage due to volume expansion after ion intercalation is an unavoidable problem; and as a typical semiconductor material, the electron conductivity per se is not ideal, which also limits its application as an electrode material for lithium ion batteries.
In recent years, in order to solve the problem of low conductivity of ferrous titanate anode materials, researchers have increased the conductivity by compounding or doping methods, such as synthesizing Nb-doped FeTiO by hydrothermal method 3 The nano sheet provides more charge carriers to participate in the conducting process by doping and introducing impurity energy level, and improves the electrochemical performance of the electrode sheet. Preparation of ilmenite FeTiO on N-doped carbon nanofiber substrate 3 A film that promotes the formation of a conductive network. FeTiO production Using composite iron and carbon 3 FeTiO is reinforced by Fe/C composite material 3 To the electron conductivity of the (b) so that the capacity during cyclingImproved results. FeTiO is modified by 3 The lithium storage performance of the lithium ion battery is improved, but the lattice mismatch of a main crystal lattice is caused after impurity atoms are introduced, meanwhile, the drift or diffusion of the impurity atoms damages the original crystal structure to form defects, and the composition does not substantially change the conductivity of the material.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide an endogenous heterojunction anode material, a preparation method thereof, a negative electrode and a lithium ion battery, so as to solve the technical problems.
The invention is realized in the following way:
in a first aspect, the present invention provides an endogenous heterojunction anode material comprising a graphene substrate and a multilayer nanoplatelet structure adhered to the graphene substrate, the multilayer nanoplatelet structure comprising a material consisting of FeTiO 3 And Fe (Fe) 2 TiO 5 An endogenous heterojunction is formed.
In a second aspect, the present invention also provides a method for preparing the endogenous heterojunction anode material, which comprises: feTiO containing cross-linking agent, graphene oxide and three-dimensional network structure 3 Dropwise adding an alkaline solution into the precursor solution of the precursor to form gel, standing and aging, drying, and reducing and sintering the dried product to form FeTiO 3 And Fe (Fe) 2 TiO 5 An endogenous heterojunction is formed.
In a third aspect, the invention also provides a negative electrode, which comprises a current collector and a negative electrode coating material coated on the current collector, wherein the negative electrode coating material comprises a conductive material, a binder and the endogenous heterojunction anode material.
In a fourth aspect, the present invention also provides a lithium ion battery, which includes a positive electrode, a separator, an electrolyte, and the negative electrode.
The invention has the following beneficial effects: feTiO adhesion with graphene as template 3 And Fe (Fe) 2 TiO 5 The anode material of the built-up endogenous heterojunction generates internal due to the charge distribution difference of the heterojunction interfaceThe battery is built to promote the migration of electron carriers, improve the conductivity of the material, accelerate the kinetics of lithium storage reaction and enable the lithium storage reaction to have excellent electrochemical performance. Further, the anode material takes graphene oxide as a substrate and forms FeTiO by sintering under a reducing atmosphere by utilizing the crosslinking performance of a crosslinking agent 3 And Fe (Fe) 2 TiO 5 The preparation method is simple to operate, the operation process is convenient to control, the synthesis components are stable, and the method innovatively utilizes oxygen-containing functional groups in graphene oxide and reducing atmosphere to induce phase change through redox synergistic effect, so that FeTiO is skillfully constructed 3 @Fe 2 TiO 5 An endogenous heterojunction. Thus, the main crystal structure is not damaged, the conductivity of the electrode material is improved, and the excellent anode material is obtained.
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In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of the preparation of a hetero-FTO according to example 1 of the present invention;
FIG. 2 is a graph of SEM characterization results of FTO and hetero-FTO according to example 1 of the present invention; wherein a is an SEM characterization result graph of the FTO, and b is an SEM characterization result graph of the HETEO-FTO;
FIG. 3 is a graph showing XRD characterization results of FTO in example 1 and GO-FTO in comparative example 1 of the present invention;
FIG. 4 is a graph showing XRD characterization results of the FTO and the hetero-FTO of example 1 of the present invention;
FIG. 5 is a graph showing TEM characterization of the HETEO-FTO of example 1 of the present invention;
FIG. 6 is a graph showing the HRTEM characterization of the HETEO-FTO of example 1 of the present invention;
FIG. 7 is a graph of FTO, GO-FTO and hetero-FTO cyclic capacities (current magnitude of 0.1A/g) for example 1 and comparative example 1 of the present invention;
FIG. 8 is a graph of the lateral flow charge and discharge (current magnitude 0.1A/g) of a HETERO-FTO according to example 1 of the present invention;
FIG. 9 is a graph of FTO and hetero-FTO cycling capacity (current magnitude 1A/g) for example 1 of the present invention;
FIG. 10 is a graph of the charge and discharge rate (current magnitude 0.1A/g-2A/g) of a hetero-FTO magnification in example 1 of the present invention;
FIG. 11 is an electrochemical impedance plot of the FTO and the hetero-FTO of example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides an endogenous heterojunction anode material, a preparation method thereof, a negative electrode and a lithium ion battery.
The inventor creatively proposes to improve the electrochemical performance of anode materials by constructing a heterostructure through a great deal of research and practice on the prior art, and potential difference at a heterojunction interface promotes induced charge redistribution, so that a built-in electric field (BIEF) is generated to reduce interface potential barrier and improve carrier mobility. The unique heterojunction structure provides an electron conduction path, promotes ion transport, increases surface reactivity, and enhances structural stability. Therefore, the following scheme is proposed.
Some embodiments of the present invention provide an endogenous heterojunction anode material comprising a graphene substrate and a multilayer nanoplatelet structure adhered to the graphene substrate, the multilayer nanoplatelet structure comprising a material consisting of FeTiO 3 And Fe (Fe) 2 TiO 5 An endogenous heterojunction is formed.
In some embodiments, the initial electrochemical capacity of the endogenous heterojunction anode material is higher than 1150mAh/g at a current density of 100mA/g, and the capacity reaches above 850mAh/g after 100 cycles. For example, at a current density of 100mA/g, the initial electrochemical capacity reaches 1207mAh/g and after 100 cycles the capacity reaches 865mAh/g.
Further, some embodiments of the present invention also provide a method of preparing the above endogenous heterojunction anode material, comprising: feTiO containing cross-linking agent, graphene oxide and three-dimensional network structure 3 Dropwise adding an alkaline solution into the precursor solution of the precursor to form gel, standing and aging, drying, and reducing and sintering the dried product to form FeTiO 3 And Fe (Fe) 2 TiO 5 An endogenous heterojunction is formed.
Specifically, in some embodiments, the method of preparing an endogenous heterojunction anode material comprises the steps of:
s1, preparing Graphene Oxide (GO).
Specifically, graphite is used as a raw material, and the improved Hummer method is adopted to prepare graphene oxide.
Illustratively, in some embodiments, 1.5-1.8 g of graphite is immersed in the concentrated sulfuric acid and the concentrated phosphoric acid and the mixed solution (the volume ratio of the concentrated sulfuric acid solution with the concentration higher than 90% to the concentrated phosphoric acid with the concentration higher than 40% is 3:0.8-1.2). Under the ice bath condition, adding 12-16 g of KMnO 4 Then transferring the mixture into a water bath (60-80 ℃) to react for 8-12 hours. Subsequently, gradually dropwise adding H into the solution system 2 O 2 And (3) neutralizing, washing with deionized water to remove acidity, and finally, putting the treated sample into a freeze dryer for freeze drying to obtain graphene oxide.
S2, preparing FeTiO 3 A precursor.
Specifically, an alkaline solution is dropped into a solution containing a titanium source and an iron source to form a gel, the gel is dried after standing and aging, and the dried product is sintered in a reducing atmosphere to obtain FeTiO 3 A precursor.
In some embodiments, the molar ratio of titanium source to iron source is 1:0.8 to 1.2, for example, 1:0.8, 1:0.9, 1:1. 1:1.1 or 1:1.2, etc.
In some embodiments, the titanium source comprises titanic acidAt least one of tetrabutyl, isobutyl titanate and n-butyl titanate. The iron source includes Fe (NO) 3 ) 3 ·9H 2 O、FeCl 3 At least one of them. The solvent used to dissolve the titanium source and the iron source is absolute ethanol. The alkaline solution is ammonia water.
Further, in some embodiments, the reduction roasting forms FeTiO 3 The precursor is carried out under the mixed atmosphere of reducing gas and inert gas, and the flow ratio of the reducing gas to the inert gas is 100ml/min: 300-500 ml/min. In some embodiments, the temperature of the reduction sintering is 400 ℃ to 600 ℃, such as 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃ or the like, the sintering time is 1h to 3h, such as 1h, 2h, 3h or the like, and the temperature rising rate is 4 ℃ to 6 ℃/min, such as 5 ℃/min. Under the condition of the reduction sintering, feTiO with better three-dimensional structure can be formed by reaction 3 A precursor.
Exemplary FeTiO preparation 3 The precursor process is as follows: tetrabutyl titanate (TBT, aba Ding Shiji) 10, ml was slowly added dropwise to 10ml of absolute ethanol and stirred to form a solution A. According to the mole ratio of iron to titanium of 1:0.8 to 1.2, fe (NO 3 ) 3 ·9H 2 O (Aba Ding Shiji) is dissolved in 30ml of absolute ethyl alcohol, a solution B is formed by full dissolution, and then the solution A and the solution B are mixed and stirred for 30-80 min to obtain a precursor solution. Dropwise adding ammonia water into the precursor to form gel, standing and aging for 12-36 h, then placing into an oven, drying at 40-100 ℃ for 24-72 h, transferring into a crucible, under the reduction and mixing sintering atmosphere of CO and Ar (the flow of CO and Ar are sequentially 100ml/min and 400 ml/min), heating to 400-600 ℃ at a heating rate of 5 ℃/min, preserving heat for 1-3 h, and cooling along with a furnace to finally obtain FeTiO 3 The precursor, designated FTO.
S3, synthesizing FeTiO 3 @Fe 2 TiO 5 And a heterojunction.
Specifically, a cross-linking agent, graphene oxide and FeTiO with a three-dimensional network structure are prepared 3 And mixing the precursors to obtain a precursor solution, then dropwise adding an alkaline solution to form gel, standing and aging, drying, and reducing and sintering the dried product.
Utilization of graphene oxide as a substrateCrosslinking agent to form precursor, sintering in reducing atmosphere to prepare FeTiO 3 @Fe 2 TiO 5 /GO anode material. Graphene oxide is used as a derivative of graphene, has excellent conductivity and high specific surface area, and a small amount of graphene oxide can be used as a template for loading anode materials under the PVP crosslinking effect. Meanwhile, under the influence of oxygen-containing functional groups and reducing atmosphere in the graphene oxide, the phase change is induced by the synergistic effect of oxidation and reduction, so that FeTiO is skillfully constructed 3 @Fe 2 TiO 5 An endogenous heterojunction. FeTiO 3 @Fe 2 TiO 5 The gradient difference of the carriers of the endogenous heterojunction interface promotes the formation of a built-in electric field (BIEF), provides power for electron conduction and ion diffusion, and obtains excellent electrochemical performance.
In some embodiments, to obtain anode materials with better electrochemical performance, a cross-linking agent, graphene oxide, and FeTiO 3 The mass ratio of the precursors is 0.4-0.8: 0.02-0.06: 10-18.
In some embodiments, the solvent of the precursor solution is absolute ethanol, and the ratio of absolute ethanol to crosslinker is 100mL:0.02g to 0.06g. For example, the crosslinker may be present in an amount of 0.02g, 0.03g, 0.04g, 0.05g, or 0.06g per 100mL of absolute ethanol. Specifically, the cross-linking agent is polyvinylpyrrolidone, and the average molecular weight is 5000-15000. The specific cross-linking agent is selected to have a better cross-linking effect, so that the heterojunction structure is formed in the reduction reaction. In some embodiments, the alkaline solution is aqueous ammonia.
Further, the time of static aging of the gelation is 12h to 36h, for example, 12h, 14h, 15h, 16h, 18h, 20h, 22h, 25h, 28h, 30h, 32h, 35h or 36h, etc. The drying temperature after static aging is 40-100 ℃, such as 40 ℃,50 ℃, 60 ℃, 70 ℃,80 ℃, 90 ℃ or 100 ℃ and the like, and the drying time is 24-72 h.
In some embodiments, the reduction sintering is performed under a mixed atmosphere of a reducing gas and an inert gas, the flow ratio of the reducing gas and the inert gas being 100ml/min: 300-500 ml/min. In some embodiments, the temperature of the reduction sintering is 400 ℃ to 600 ℃, such as 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃ or the like, the sintering time is 1h to 3h, such as 1h, 2h, 3h or the like, and the temperature rising rate is 4 ℃ to 6 ℃/min, such as 5 ℃/min.
Illustratively, in some embodiments, feTiO is synthesized 3 @Fe 2 TiO 5 The specific operation of the heterojunction is as follows: mixing uniformly dispersed graphene oxide and polyvinylpyrrolidone mixed solution with FeTiO 3 And mixing the precursors, and stirring for 1-4 hours to form a precursor solution. Dropwise adding ammonia water into the precursor solution to form gel, standing and aging for 12-36 h, then placing into an oven, drying at 40-100 ℃ for 24-72 h, transferring into a crucible, under the reduction and mixing sintering atmosphere of CO and Ar (the flow of CO and Ar are sequentially 100ml/min and 400 ml/min), heating to 400-600 ℃ at a heating rate of 5 ℃/min, preserving heat for 1-3 h, and cooling along with a furnace to finally obtain the FeTiO with FeTiO 3 @Fe 2 TiO 5 The anode material of the heterojunction is denoted as heterofto.
The preparation process of the uniformly dispersed mixed solution of graphene oxide and polyvinylpyrrolidone comprises the following steps: mixing 0.02-0.06 g of prepared GO and 0.4-0.8 g of polyvinylpyrrolidone (PVP, average molecular weight 10000, aba Ding Shiji) in 100ml of absolute ethyl alcohol, and carrying out ultrasonic vibration for 2-4 hours to uniformly disperse the mixture.
Some embodiments of the present invention also provide a negative electrode comprising a current collector and a negative electrode coating material coated on the current collector, the negative electrode coating material comprising a conductive material, a binder, and the endogenous heterojunction anode material of the embodiments described above.
Some embodiments of the present invention also provide a lithium ion battery comprising a positive electrode, a separator, an electrolyte, and the negative electrode described above.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides an endogenous heterojunction anode material and a preparation method thereof, wherein the preparation steps of the endogenous heterojunction anode material comprise:
(1) Preparation of Graphene Oxide (GO): with 99% pure stoneThe ink is used as a raw material to prepare Graphene Oxide (GO) through a modified Hummer method. 1.5g of graphite was immersed in a mixed solution of concentrated sulfuric acid and concentrated phosphoric acid (a concentrated sulfuric acid solution having a concentration of 95% and a concentrated phosphoric acid solution having a concentration of 50% in a volume ratio of 3:1). Under ice bath conditions, 15g of KMnO was added 4 It was then transferred to a water bath (60 ℃) for 10h. Subsequent gradual drop-in of H 2 O 2 And neutralizing, removing acidity through ion washing, and finally, putting the treated sample into a freeze dryer for freeze drying to obtain graphene oxide.
(2) Preparing a mixed dispersion liquid of polyvinylpyrrolidone and graphene: mixing 0.03g of prepared GO and 0.5g of polyvinylpyrrolidone (PVP, average molecular weight 10000, aba Ding Shiji) in 100ml of absolute ethyl alcohol, and carrying out ultrasonic vibration for 2 hours to uniformly disperse the mixture.
(3) Synthesis of FeTiO 3 Precursor: tetrabutyl titanate (TBT, aba Ding Shiji) 10, ml was slowly added dropwise to 10ml of absolute ethanol and stirred to form a solution A. According to the mole ratio of iron to titanium of 1:1, fe (NO) 3 ) 3 ·9H 2 O (Aba Ding Shiji) is dissolved in 30ml of absolute ethanol, fully dissolved to form a solution B, and then the solution A and the solution B are mixed and stirred for 30min to obtain a precursor solution. Dropwise adding ammonia water into the precursor to form gel, standing and aging for 12h, then placing into an oven, drying at 100 ℃ for 24h, transferring into a crucible, under the reduction and mixing sintering atmosphere of CO and Ar (the flow rate of CO and Ar is 100ml/min and 400ml/min in sequence), heating to 500 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, and cooling along with the oven to finally obtain FeTiO 3 The precursor, designated FTO.
(4) Synthesis of FeTiO 3 @Fe 2 TiO 5 Heterojunction: mixing the uniformly dispersed graphene oxide and polyvinylpyrrolidone mixed solution prepared in the step (2) with FeTiO 3 The precursors were mixed and stirred for 1h to form a precursor solution. Dropwise adding ammonia water into the precursor solution to form gel, standing and aging for 12h, then placing into an oven, drying at 100deg.C for 24h, transferring into a crucible, and under CO and Ar reduction mixed sintering atmosphere (CO and Ar flow are sequentially 100ml/min and 400 ml/min), heating to 500deg.C at a heating rate of 5deg.C/minAnd preserving heat for 2 hours, and cooling along with a furnace to finally obtain the FeTiO with the FeTiO 3 @Fe 2 TiO 5 The anode material of the heterojunction is denoted as heterofto.
Wherein FeTiO is prepared 3 @Fe 2 TiO 5 The flow of the heterojunction is shown in figure 1. Through the figure 1, the preparation and formation process of the heterofto, using PVP as a sacrificial template, the precursor and the GO template form a stable cross-linked network under the action of ammonia. The sample is sintered by reducing gas, and the surface of the precursor is reduced to FeTiO 3 Grow inwards, and the graphene oxide functional group is internal Fe 2 TiO 5 The phase transition provides oxidative power, inducing co-promotion of heterogeneous nucleation. In the sintering process, GO is removed from the functional group, PVP is decomposed at high temperature, and FeTiO is finally formed 3 @Fe 2 TiO 5 /GO anode material.
Example 2
The embodiment provides an endogenous heterojunction anode material and a preparation method thereof, wherein the preparation steps of the endogenous heterojunction anode material comprise:
(1) Preparation of Graphene Oxide (GO): graphite with the purity of 99% is used as a raw material, and Graphene Oxide (GO) is prepared by a modified Hummer method. 1.6g of graphite was immersed in a mixed solution of concentrated sulfuric acid and concentrated phosphoric acid (a concentrated sulfuric acid solution having a concentration of 95% and a concentrated phosphoric acid solution having a concentration of 50% in a volume ratio of 3:0.8). Under ice bath conditions, 12g of KMnO was added 4 It was then transferred to a water bath (70 ℃ C.) for 8h of reaction. Subsequent gradual drop-in of H 2 O 2 And neutralizing, removing acidity through ion washing, and finally, putting the treated sample into a freeze dryer for freeze drying to obtain graphene oxide.
(2) Preparing a mixed dispersion liquid of polyvinylpyrrolidone and graphene: 0.05g of the prepared GO and 0.4g of polyvinylpyrrolidone (PVP, average molecular weight 10000, aba Ding Shiji) are mixed in 100ml of absolute ethyl alcohol, and the mixture is subjected to ultrasonic vibration for 1h to uniformly disperse the mixture.
(3) Synthesis of FeTiO 3 Precursor: tetrabutyl titanate (TBT, aba Ding Shiji) 10, ml was slowly added dropwise to 10ml of absolute ethanol and stirred to form a solution A. According to ironTitanium molar ratio 1:0.8, fe (NO) 3 ) 3 ·9H 2 O (Aba Ding Shiji) is dissolved in 30ml of absolute ethanol, fully dissolved to form a solution B, and then the solution A and the solution B are mixed and stirred for 50min to obtain a precursor solution. Dropwise adding ammonia water into the precursor to form gel, standing and aging for 24 hours, then placing into an oven, drying at 80 ℃ for 42 hours, transferring into a crucible, under the reduction and mixing sintering atmosphere of CO and Ar (the flow rate of CO and Ar is 100ml/min and 400ml/min in sequence), heating to 450 ℃ at a heating rate of 4 ℃/min, preserving heat for 3 hours, and cooling along with the oven to finally obtain FeTiO 3 The precursor, designated FTO.
(4) Synthesis of FeTiO 3 @Fe 2 TiO 5 Heterojunction: mixing the uniformly dispersed graphene oxide and polyvinylpyrrolidone mixed solution prepared in the step (2) with FeTiO 3 The precursors were mixed and stirred for 1h to form a precursor solution. Dropwise adding ammonia water into the precursor solution to form gel, standing and aging for 24 hours, then placing into an oven, drying at 80 ℃ for 24 hours, transferring into a crucible, under the reduction and mixing sintering atmosphere of CO and Ar (the flow rates of CO and Ar are sequentially 100ml/min and 400 ml/min), heating to 450 ℃ at a heating rate of 4 ℃/min, preserving heat for 3 hours, and cooling along with the oven to finally obtain the FeTiO composite material 3 @Fe 2 TiO 5 The anode material of the heterojunction is denoted as heterofto.
Example 3
The embodiment provides an endogenous heterojunction anode material and a preparation method thereof, wherein the preparation steps of the endogenous heterojunction anode material comprise:
(1) Preparation of Graphene Oxide (GO): graphite with the purity of 99% is used as a raw material, and Graphene Oxide (GO) is prepared by a modified Hummer method. 1.8g of graphite was immersed in a mixed solution of concentrated sulfuric acid and concentrated phosphoric acid (a concentrated sulfuric acid solution having a concentration of 95% and a concentrated phosphoric acid solution having a concentration of 50% in a volume ratio of 3:1.2). Under ice bath conditions 16g KMnO was added 4 It was then transferred to a water bath (80 ℃) for 8h of reaction. Subsequent gradual drop-in of H 2 O 2 And neutralizing, removing acidity through ion washing, and finally, putting the treated sample into a freeze dryer for freeze drying to obtain graphene oxide.
(2) Preparing a mixed dispersion liquid of polyvinylpyrrolidone and graphene: 0.06g of prepared GO and 0.8g of polyvinylpyrrolidone (PVP, average molecular weight 10000, aba Ding Shiji) are mixed in 100ml of absolute ethyl alcohol, and the mixture is subjected to ultrasonic vibration for 1h to uniformly disperse the mixture.
(3) Synthesis of FeTiO 3 Precursor: tetrabutyl titanate (TBT, aba Ding Shiji) 10, ml was slowly added dropwise to 10ml of absolute ethanol and stirred to form a solution A. According to the mole ratio of iron to titanium of 1:1.2, fe (NO) 3 ) 3 ·9H 2 O (Aba Ding Shiji) is dissolved in 30ml of absolute ethanol, fully dissolved to form a solution B, and then the solution A and the solution B are mixed and stirred for 80min to obtain a precursor solution. Dropwise adding ammonia water into the precursor to form gel, standing and aging for 36h, then placing into an oven, drying at 50 ℃ for 72h, transferring into a crucible, under the mixed sintering atmosphere of CO and Ar reduction (the flow rate of CO and Ar is 100ml/min and 400ml/min in sequence), heating to 600 ℃ at a heating rate of 6 ℃/min, preserving heat for 1h, and cooling along with the oven to finally obtain FeTiO 3 The precursor, designated FTO.
(4) Synthesis of FeTiO 3 @Fe 2 TiO 5 Heterojunction: mixing the uniformly dispersed graphene oxide and polyvinylpyrrolidone mixed solution prepared in the step (2) with FeTiO 3 The precursors were mixed and stirred for 1h to form a precursor solution. Dropwise adding ammonia water into the precursor solution to form gel, standing and aging for 24 hours, then placing into an oven, drying at 50 ℃ for 72 hours, transferring into a crucible, under the reduction and mixing sintering atmosphere of CO and Ar (the flow rates of CO and Ar are sequentially 100ml/min and 400 ml/min), heating to 600 ℃ at a heating rate of 6 ℃/min, preserving heat for 1 hour, and cooling along with the oven to finally obtain the FeTiO-containing material 3 @Fe 2 TiO 5 The anode material of the heterojunction is denoted as heterofto.
Comparative example 1
The embodiment provides an endogenous heterojunction anode material and a preparation method thereof, wherein the preparation steps of the endogenous heterojunction anode material comprise:
(1) Preparation of Graphene Oxide (GO): graphite oxide prepared from graphite with purity of 99% by improved Hummer methodAlkene (GO). 1.5g of graphite was immersed in a mixed solution of concentrated sulfuric acid and concentrated phosphoric acid (the volume ratio of concentrated sulfuric acid solution with a concentration higher than 90% to concentrated phosphoric acid with a concentration higher than 40% was 3:1). Under ice bath conditions, 15g of KMnO was added 4 It was then transferred to a water bath (60 ℃) for 10h. Subsequent gradual drop-in of H 2 O 2 And neutralizing, removing acidity through ion washing, and finally, putting the treated sample into a freeze dryer for freeze drying to obtain graphene oxide.
(2) Preparing graphene mixed dispersion liquid: mixing 0.03g of prepared GO in 100ml of absolute ethyl alcohol, and carrying out ultrasonic oscillation for 2 hours to uniformly disperse the GO.
(3) Synthesis of FeTiO 3 Precursor: tetrabutyl titanate (TBT, aba Ding Shiji) 10, ml was slowly added dropwise to 10ml of absolute ethanol and stirred to form a solution A. According to the mole ratio of iron to titanium of 1:1, fe (NO) 3 ) 3 ·9H 2 O (Aba Ding Shiji) is dissolved in 30ml of absolute ethanol, fully dissolved to form a solution B, and then the solution A and the solution B are mixed and stirred for 30min to obtain a precursor solution. Dropwise adding ammonia water into the precursor to form gel, standing and aging for 12h, then placing into an oven, drying at 100 ℃ for 24h, transferring into a crucible, under the reduction and mixing sintering atmosphere of CO and Ar (the flow rate of CO and Ar is 100ml/min and 400ml/min in sequence), heating to 500 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, and cooling along with the oven to finally obtain FeTiO 3 The precursor, designated FTO.
(4) Synthesis of FeTiO 3 @Fe 2 TiO 5 Heterojunction: mixing the graphene mixed dispersion liquid prepared in the step (2) with FeTiO 3 The precursors were mixed and stirred for 1h to form a precursor solution. Dropwise adding ammonia water into the precursor solution to form gel, standing and aging for 12 hours, then placing into an oven, drying at 100 ℃ for 24 hours, transferring into a crucible, under the reduction and mixing sintering atmosphere of CO and Ar (the flow rates of CO and Ar are sequentially 100ml/min and 400 ml/min), heating to 500 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, and cooling along with the oven to finally obtain the anode material FeTiO 3 GO, designated GO-FTO.
Test example 1
SEM characterization was performed on the FTO and the hetero-FTO obtained in example 1, and the results are shown in FIG. 2. As can be seen from FIG. 2, there is a clear difference in morphology of the FTO and the hetero-FTO samples, the FTO being typical nanosphere particles, while the hetero-FTO exhibits a lamellar multilayer structure.
XRD characterization was further performed on the FTO and the hetero-FTO obtained in example 1 and the GO-FTO in comparative document 1, and the characterization results of the FTO were compared with the GO-FTO and the hetero-FTO, respectively, and the comparison results are shown in FIG. 3 and FIG. 4. As can be seen from FIG. 3, the FTO diffraction peak positions are about the same, and the GO-FTO sample diffraction peak is slightly sharp, but no new phase appears. As can be seen from FIG. 4, the diffraction peak of the FTO corresponds to PDF card PDF#75-0519, and belongs to the R-3 (148) lattice triclinic crystal structure. Diffraction peaks 2 theta of the hetero-FTO sample are 25.49 degrees, 32.56 degrees and 35.27 degrees respectively correspond to Fe 2 TiO 5 PDF #76-1158 (110) crystal plane and FeTiO 3 PDF #75-0519 (112), (-110) crystal planes. The phase composition of the two electrode materials was determined.
The results of TEM transmission electron microscope characterization of the HETEO-FTO obtained in example 1 are shown in FIG. 5. FIG. 5 shows that the HETEO-FTO is adhered to the graphene sheet in the TEM image, and the nano-platelet structure is more evident.
The HRTEM characterization was further performed on the HETEO-FTO obtained in example 1, and the results are shown in FIG. 6. FIG. 6 shows that the HRTEM image observes middle FeTiO 3 (120) crystal face and Fe 2 TiO 5 FeTiO is formed on the (113) crystal face 3 And FeTiO 3 @Fe 2 TiO 5 Heterojunction, XRD results were further confirmed.
Test example 2
The FTO and the hetero-FTO obtained in the example 1 and the GO-FTO in the comparative example 1 are taken as anode materials and are fully ground and mixed with acetylene black in a mortar, sodium Alginate (SA) is added for further grinding and mixing, and the mass ratio of the three materials is 8:1:1. and (3) dropwise adding deionized water to prepare slurry, coating the slurry on the copper foil special for the anode, drying the copper foil in a vacuum drying oven at 80 ℃ for 12 hours, and taking out the copper foil for cutting. The electrolyte is composed of 1mol/L LiPF 6 And EC: DMC: DEC (volume ratio 1:1:1). A polypropylene (PP) microporous membrane is used as the separator,the lithium metal sheet serves as an electrode. Finally, the 2032 type button cell was assembled in an argon protected glove box. And (3) connecting the assembled electrode plate into a blue electric testing system, setting a voltage window to 0.01-3V, selecting the current density to 0.1A/g, and testing the cross flow charge-discharge cycle. And continuously setting the current density to be 0.1A/g-2A/g, and testing the charge-discharge cycle of the multiplying power.
Wherein FIG. 7 is a graph of FTO, GO-FTO and hetero-FTO cyclic capacities (current magnitude 0.1A/g); FIG. 8 is a graph of a lateral flow charge-discharge curve (current magnitude 0.1A/g) for a hetero-FTO; FIG. 9 is a graph of FTO and hetero-FTO cyclic capacity (current magnitude 1A/g); FIG. 10 is a graph of a HETERO-FTO magnification charge-discharge curve (current magnitude 0.1A/g-2A/g); FIG. 11 is an electrochemical impedance plot of FTO and hetero-FTO.
FIG. 7 shows that the initial capacity of the HETEO-FTO reaches 1207mAh/g 2 times that of the FTO (600 mAh/g), and that the initial capacity of the GO-FTO is 794mAh/g far less than that of the HETEO-FTO. After 100 cycles of testing, the HETEO-FTO still exhibited a high capacity performance of 865.9mAh/g, while the GO-FTO capacity was decayed to 573mAh/g and the FTO capacity was decayed to 377mAh/g.
Fig. 8 shows that the charge-discharge plateau of the constant current charge-discharge curve changes significantly as the cycle proceeds.
FIG. 9 shows that at a current density of 1A/g, the capacity of the hetero-FTO after 400 cycles was 261.3mAh/g, which is still far superior to the FTO (97.3 mAh/g).
FIG. 10 shows that the discharge capacities of the hetero-FTO are 1109, 750, 570, 394 and 251mAh/g, respectively, with current densities from 100, 200, 400, 1000 to 2000 mAh/g. When the current density was restored to 100mAh/g after multiple cycles, a reversible capacity of 889mAh/g was still provided, indicating that GO-FTO exhibited excellent rate capability.
FIG. 11 shows that the Nyquist ring of the HETER-FTO is smaller than the FTO and therefore has a smaller internal resistance.
In summary, feTiO was constructed using PVP-crosslinked GO as a template 3 @Fe 2 TiO 5 Endogenous heterojunction anode material (hetero-FTO). Due to the difference of charge distribution of heterojunction interfaces, the generated built-in electric field promotes the migration of electron carriers, improves the material conductivity and accelerates the storageLithium reaction kinetics, which gives it excellent electrochemical properties. Compared with the Fe-Ti-O based electrode material reported in the past, the heterojunction-containing anode material (heter-FTO) obtains remarkably excellent lithium electrical property, and the initial electrochemical capacity of the material reaches 1207mA/g under the current density of 100mA/g, thus being FeTiO 3 (600 mA/g) 2 times. The capacity still reached 865mA/g after 100 cycles.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. An endogenous heterojunction anode material, characterized in that it comprises a graphene substrate and a multilayer nanoplatelet structure adhered to the graphene substrate, the multilayer nanoplatelet structure comprising a polymer formed from FeTiO 3 And Fe (Fe) 2 TiO 5 An endogenous heterojunction is formed.
2. The endogenous heterojunction anode material of claim 1, wherein the initial electrochemical capacity is above 1150mAh/g at a current density of 100mA/g and the capacity after 100 cycles is above 850mAh/g.
3. A method of preparing an endogenous heterojunction anode material as claimed in claim 1 or 2, comprising: feTiO containing cross-linking agent, graphene oxide and three-dimensional network structure 3 Dropwise adding an alkaline solution into the precursor solution of the precursor to form gel, standing and aging, drying, and reducing and sintering the dried product to form FeTiO 3 And Fe (Fe) 2 TiO 5 An endogenous heterojunction is formed.
4. The method according to claim 3, wherein the crosslinking agent, the graphene oxide and the FeTiO 3 Mass ratio of precursor0.4 to 0.8: 0.02-0.06: 10-18;
and/or, the solvent of the precursor solution is absolute ethyl alcohol, and the dosage ratio of the absolute ethyl alcohol to the crosslinking agent is 100mL:0.02 g-0.06 g;
and/or the cross-linking agent is polyvinylpyrrolidone, and the average molecular weight is 5000-15000;
and/or, the alkaline solution is ammonia water;
and/or the graphene oxide is prepared from graphite by a modified Hummer method.
5. The method according to claim 3, wherein the stationary aging time is 12 to 36 hours;
and/or the drying temperature is 40-100 ℃ and the drying time is 24-72 h;
and/or, the reduction sintering is performed under a mixed atmosphere of a reducing gas and an inert gas, wherein the flow ratio of the reducing gas to the inert gas is 100ml/min: 300-500 ml/min;
and/or reducing and sintering at 400-600 ℃ for 1-3 hours;
and/or the temperature rising rate of the reduction sintering is 4-6 ℃/min.
6. The method according to any one of claims 3 to 5, wherein FeTiO having a three-dimensional network structure 3 The precursor is mainly prepared by the following steps:
dropwise adding an alkaline solution into a solution containing a titanium source and an iron source to form a gel, standing and aging, drying, and sintering the dried product in a reducing atmosphere to obtain the FeTiO 3 A precursor.
7. The method of claim 6, wherein the titanium source and the iron source have a molar ratio of iron to titanium of 1: 0.8-1.2;
and/or the titanium source comprises at least one of tetrabutyl titanate, isobutyl titanate and n-butyl titanate;
and/or, theThe iron source includes Fe (NO) 3 ) 3 ·9H 2 O、FeCl 3 At least one of (a) and (b);
and/or the solvent used for dissolving the titanium source and the iron source is absolute ethyl alcohol.
8. The method according to claim 6, wherein the dried product is sintered in a reducing atmosphere to obtain FeTiO 3 The precursor is carried out under the mixed atmosphere of reducing gas and inert gas, and the flow ratio of the reducing gas to the inert gas is 100ml/min: 300-500 ml/min; and/or reducing and sintering at 400-600 ℃ for 1-3 hours; and/or the heating rate is 4-6 ℃/min.
9. A negative electrode comprising a current collector and a negative electrode coating material coated on the current collector, the negative electrode coating material comprising a conductive material, a binder, and the endogenous heterojunction anode material of claim 1 or 2.
10. A lithium ion battery comprising a positive electrode, a separator, an electrolyte, and the negative electrode of claim 9.
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CN104051729A (en) * 2014-07-04 2014-09-17 电子科技大学 Preparation method of NiFe2O4/graphene composite material for lithium battery cathode
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