CN102201574B - Oxygen-vacancy-containing lithium ferrous silicate and carbon composite anode material and preparation method - Google Patents

Oxygen-vacancy-containing lithium ferrous silicate and carbon composite anode material and preparation method Download PDF

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CN102201574B
CN102201574B CN2011100928238A CN201110092823A CN102201574B CN 102201574 B CN102201574 B CN 102201574B CN 2011100928238 A CN2011100928238 A CN 2011100928238A CN 201110092823 A CN201110092823 A CN 201110092823A CN 102201574 B CN102201574 B CN 102201574B
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木士春
杨金龙
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Wuhan University of Technology WUT
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Abstract

The invention relates to a secondary lithium battery anode composite material, in particular to an oxygen-vacancy-containing lithium ferrous silicate and carbon composite material. The chemical formula of the composite material is Li2FeSiO4-xNy/C, wherein x is more than 0 and less than or equal to 1, y is more than 0 and less than or equal to 0.5, the condition that x is more than or equal to 3y/2 is met, and carbon content is 5-20wt%. The intrinsic conductivity and the lithium ion conductivity inside granules of the composite material are high, and the composite material has excellent performances such as high capacity and high multiplying power. The preparation method of the composite material comprises the steps of: preparing sol from lithium salt, ferrous salt, a silicon source and a carbon source and then carrying out high temperature calcination on the sol twice to obtain granular and oxygen-vacancy-containing lithium ferrous silicate and carbon composite material.

Description

A kind of oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite anode material and preparation method
Technical field
The present invention relates to energy industry secondary cell ferrosilicon silicate of lithium and carbon composite and preparation method, particularly relate to oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite and the preparation method of chemical property excellence.
Background technology
Lithium-ion-power cell is progressively substituting conventional batteries, image drift mobile phone, notebook computer, camera, the uses such as video camera all be lithium ion battery, the lithium-ion electric motor-car also comes into the market, the performance of its battery depends primarily on the performance of positive electrode.Anton Nyte ' n etc. utilized the Li that synthesized of solid phase method success in 2005 2FeSiO 4As anode material for lithium-ion batteries, reported that it is the orthohormbic structure of polyanion type.Its characteristics are summarized as follows: 1) functional during high temperature: internal temperature is then up to 95 ℃ during 65 ℃ of external temperatures, and temperature can reach 160 ℃, the structural safety of battery, intact when battery discharge finished; 2) even inside battery or outside come to harm, burning and blast can not occur in battery, fail safe is good; 3) fabulous cycle life, through 500 circulations, its discharge capacity is still greater than 95%; 4) overdischarge is arrived zero volt also without damaging; 5) low cost; 6) environmentally safe.Compare with cathode material of lithium iron phosphate lithium battery, ferrosilicon silicate of lithium has lower bandwidth (electronegativity of Si is lower than P, and the ferroelectric right current potential of ferrous iron and trivalent reduces), has relatively high conductivity.And ferrosilicon silicate of lithium has taking off of two lithium ions and owes in theory, if can seek the good electrolyte of potential stability, the granular size of control material is in the nanoscale scope, can reach to surpass a lithium ion and take off the specific capacity of owing.But because the restriction of the ferrosilicon silicate of lithium 3-D solid structure of rhombic system, its electronic conductivity and lithium ion diffusion rate are lower, and this is its one barrier that is applied to power battery material.Mostly adopt at present carbon to coat and metal-doped its chemical property that improves.Its synthetic method mainly contains: high temperature solid-state method, sol-gal process, hydro-thermal assisting sol gel method, microwave method etc.
The people such as Anton Nyte ' n adopt solid phase method to synthesize Li 2FeSiO 4With ferrous salt and Li at first 2SiO 3Be blended in by chemical ratios that high temperature sintering forms under the protection gas, although method is simple, it is exactly that material grains after synthetic is large that the method has common shortcoming, skewness.
Sol-gal process synthesizes Li 2FeSiO 4R.Dominko, M.Bele,
Figure BDA0000055221290000011
Mix by certain chemical ratios with ironic citrate and ferric nitrate in 2006 Deng the people; high temperature sintering forms colloidal sol under protective atmosphere; and then add a certain proportion of lithium hydroxide and silicon dioxide mixing, and the xerogel that heat tracing obtains under protective atmosphere and hydrothermal condition, at last grinding forms.The advantage of the method is that the material granule that obtains has good uniformity, but complex process is wayward.
The Yang Yong of Xiamen University (number of patent application 2006100005329.2) uses hydro-thermal assisting sol gel method; with lithium acetate, ferric acetate and positive silicic acid second vinegar hydrothermal treatment consists 24h in the mixed liquor of second alcohol and water; mix with the sucrose ball milling after the wet gel drying that obtains, then 600 ℃ of sintering 10h obtain Li under nitrogen protection 2FeSiO 4/ C composite nano materials.The material phase purity that the method obtains is high, and granular size is 40-80nm, and high rate performance is good.
Although these composite material volumetric properties are high, high rate performance is good, still can't be applied to electrokinetic cell.Electrokinetic cell not only requires electric conductivity good between the particle and lithium ion transmission performance, and requires the intrinsic conductivity of its granule interior and the lithium ion conducting rate also should be all better, could obtain it and require higher high rate performance.
At present, for Li 2FeSiO 4The research that these shortcomings of material are launched is a lot, and for example metal-doped in lithium position and the employing of iron position, it all preferably resolves Li 2FeSiO 4This shortcoming of material.After solving, these problems believe Li 2FeSiO 4Good application prospect will be arranged in electrokinetic cell market.
Summary of the invention
The present invention is different from background technology, in order to overcome Li 2FeSiO 4The intrinsic conductivity of material and lithium ion transmission rate are hanged down problem, and a kind of oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite and preparation method thereof are provided.Solve material stacking density by crystal formation control growth, adopt simultaneously the method can well protect ferrous oxidation, its cost is low, and technique is simple, is easy to realize industrialization.
Technical scheme of the present invention is to adopt gas phase, liquid phase, and solid phase nitrogenous source doping nitrogen unit usually part replaces Li 2FeSiO 4In oxygen, control the charge balance of material internal by lithium ion content, it is a kind of based on serondary lithium battery oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite anode material to utilize collosol and gel and high temperature solid-state method to synthesize, its chemical expression is: Li 2FeSiO 4-xN y/ C, wherein 0＜x≤1,0＜y≤0.5, and the x 〉=3y/2 that satisfies condition.This composite positive pole has higher volumetric properties, and lower bulk density and high high rate performance are specially adapted to electrokinetic cell.
The present invention is based on the preparation method of serondary lithium battery oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite anode material, may further comprise the steps:
1) with the divalence source of iron, the ratio 1: 1 of amount of substance is pressed in the silicon source, fully be blended at least a solvent in water, absolute ethyl alcohol, the acetone with the liquid or solid of doping nitrogen source or gas, its gas nitrogenous source is controlled by controlled atmospher, regulates the pH value between 7-12, vigorous stirring 1-24h, carbon source with lithium source and reproducibility adds again, controls temperature at 70-160 ℃, vigorous stirring 1-48h, obtain front aggressiveness colloidal sol, aggressiveness xerogel before oven dry obtains under 60-150 ℃ temperature;
2) adopt the secondary high-temperature solid phase method, front aggressiveness xerogel speed with 1-20 ℃/min under inert atmosphere or reducing atmosphere is heated to 300-500 ℃ of constant temperature 1-24h, again with the cooling of the speed of 1-20 ℃/min or naturally cool to room temperature, with pressed powder, calcine 1-48h with 600-850 ℃ temperature again, after being down to room temperature, namely get oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite Li 2FeSiO 4-xN y/ C powder, wherein 0＜x≤1,0＜y≤0.5.
Among the preparation method of the present invention, described lithium source is lithium hydroxide, lithium acetate, lithium carbonate, lithium chloride, lithium sulfate or lithium nitrate.
Described divalence source of iron is ferrous oxalate, ferrous acetate, frerrous chloride, ferrous nitrate, ferrous carbonate, ferrous lactate or ferrous sulfate.
Described silicon source is methyl silicate or tetraethoxysilane.
Described carbon source is glucose, sucrose, acetylene black, carbon black or carbon gel, and its content is 5wt%-20wt%.
Among the preparation method of the present invention, the nitrogenous source of described doping is lithium nitride, lithium nitrate, ethylenediamine, tetramethylethylenediamine, NEED, nitrogen or ammonia.
Preparation method's step 2 of the present invention) in, described atmosphere is nitrogen, ammonia, argon gas, nitrogen hydrogen mixeding gas, argon hydrogen mixture or carbon monoxide and carbon dioxide gas mixture.
Among the preparation method of the present invention, described pH value is regulated with lithium hydroxide, NaOH, potassium hydroxide or ammoniacal liquor.
Among the preparation method of the present invention, described solvent is absolute ethyl alcohol or acetone.
Preparation method's step 1 of the present invention) lithium source in, divalence source of iron, the mol ratio in silicon source are lithium: iron: silicon=2: 1: 1.
The method adopts solid phase method to combine with sol method, selects cost of material cheap, and operating procedure is simple, is easy to industrialization, can effectively prevent the ferrous iron generation oxidation in the building-up process.Because the transmission of lithium ion in lattice is subject to tetrahedron SiO 4Impact, work as SiO 4After oxygen lacks in the tetrahedron, the Coulomb force that lithium ion is subject in lattice reduces, and migration rate can improve, and the present invention adopts the lower nitrogen of negative valency attitude to replace oxygen, two nitrogen form an oxygen room after replacing two oxygen, thereby improve intrinsic conductivity and the lithium ion transmission rate of material.Remaining carbon can strengthen the conductivity between the particle simultaneously, and the nitrogen source compound of doping can effectively be controlled the oriented growth of crystal grain, can prepare particle diameter and arrive certain uniform oxygen-containing vacancy ferrosilicon silicate of lithium and the carbon composite of hundreds of nanometers shape tens.The material that utilizes the present invention to prepare has higher discharge capacity, and high rate performance has extraordinary use value preferably, is particularly suitable for electrokinetic cell.
Description of drawings
The field emission scanning electron microscope figure of composite material among Fig. 1 embodiment 1
Composite material turns target XRD collection of illustrative plates among Fig. 2 embodiment 1
Be prepared into the charging and discharging curve that serondary lithium battery records among Fig. 3 embodiment 1, charge-discharge magnification is 5C
Below in conjunction with embodiment the present invention is further set forth.The following example scheme all just illustrates, all in the present invention or the change that is equal in the scope of the present invention all be included in the invention.
Embodiment
Embodiment 1
With 1.799 gram FeC 2O 42H 2O and 2.08 gram Si (OC 2H 5) 4Mix, join in the absolute ethyl alcohol of ethylenediamine (accounting for 20wt%) of 150ml, pH value is controlled at 9, behind the room temperature vigorous stirring 6h, adds 2.04 gram LiAc2H 2O and 0.2 gram glucose are warmed up to 80 ℃ of insulation 12h, then obtain xerogel 100 ℃ of oven dry.It is transferred in the porcelain boat in tube type resistance furnace at Ar/H 2(H 2Account for volume 3%) under, the speed with 5 ℃/min is heated to 400 ℃ of constant temperature 12, h first, speed with 5 ℃/min cools to room temperature again, and taking-up at compressing tablet, is calcined 24h with 700 ℃ temperature with powder again, naturally be down to room temperature, obtain oxygen-containing vacancy ferrous metasilicate lithium/carbon composite material.It is rhombic system to resulting materials by turning the target XRD analysis, and space group is Pmn21.Observing particle diameter by field emission scanning electron microscope is bulk crystals about 500nm, and XPS characterizes to get x=0.35, y=0.21, and composite material developed by molecule formula is Li 2FeSiO 3.65N 0.21/ C.
The chemical property of gained sample is measured by the following method: the Li that weighing 0.75 gram oxygen-containing vacancy ferrosilicon silicate of lithium and carbon are compound 2FeSiO 3.65N 0.21/ C active material, add 0.15 gram acetylene black as conductive agent, add again quality and be the aqueous solution of 10% isopropyl alcohol as the PTFE binding agent of solvent preparation, add the 2ml isopropyl alcohol as dispersant, after the sealing on star-like formula ball mill with the speed ball milling 4h of 500rpm, then get slurry and be pressed into thin slice with roll squeezer, the sequin that radius is 0.5cm is made in oven dry, claim to force together in nickel foam after its quality, make anodal disk.Take lithium metal as negative pole, with the LiPF of 1.0mol/L 6/ EC+DMC (1: 1) is electrolyte, and the celgard2300 thin slice is barrier film, is assembled into the CR2025 button cell in being full of the glove box of argon gas, at one night of ageing, carries out charge-discharge test.
Fig. 3 has provided 1-20 charging and discharging curve under the 5C multiplying power, and voltage range is 1.5-4.8V, and the discharge capacity that obtains is 128mAh/g, is stabilized in about 120mAh/g subsequently.
Embodiment 2
With 1.24 gram FeAc 24H 2O and 2.08 gram Si (OC 2H 5) 4Mix, join in the absolute ethyl alcohol of NEED (accounting for 20wt%) of 150ml, pH value is controlled at 10, behind the room temperature vigorous stirring 12h, adds 2.04 gram LiAc2H 2O and 0.3 gram glucose are warmed up to 90 ℃ of insulation 24h, then obtain xerogel 100 ℃ of oven dry.It is transferred in the porcelain boat in tube type resistance furnace at Ar/H 2Under (Ar accounts for volume 3%), the speed with 5 ℃/min is heated to 450 ℃ of constant temperature 12, h first, speed with 5 ℃/min cools to room temperature again, and taking-up at compressing tablet, is calcined 24h with 750 ℃ temperature with powder again, naturally be down to room temperature, obtain oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite Li 2FeSiO 3.78N 0.13/ C.
The chemical property of gained sample is measured by the following method: the Li that weighing 0.75 gram oxygen-containing vacancy ferrosilicon silicate of lithium and carbon are compound 2FeSiO 3.78N 0.13/ C active material, add 0.15 gram acetylene black as conductive agent, add again quality and be the aqueous solution of 10% isopropyl alcohol as the PTFE binding agent of solvent preparation, add the 2ml isopropyl alcohol as dispersant, after the sealing on star-like formula ball mill with the speed ball milling 4h of 500rpm, then get slurry and be pressed into thin slice with roll squeezer, the sequin that radius is 0.5cm is made in oven dry, claim to force together in nickel foam after its quality, make anodal disk.Take lithium metal as a negative pole, with the LiPF of 1.0mol/L 6/ EC+DMC (1: 1) is electrolyte, and the celgard2300 thin slice is barrier film, is assembled into the CR2025 button cell in being full of the glove box of argon gas, at one night of ageing, carries out charge-discharge test.
Embodiment 3
With 2.88 gram FeC 3H 10O 3With 2.08 gram Si (OC 2H 5) 4Mix, join in the absolute ethyl alcohol of tetramethylethylenediamine (accounting for 20wt%) of 150ml, pH value is controlled at 8.5, behind the room temperature vigorous stirring 6h, adds 2.04 gram LiAc2H 2O and 0.1 gram glucose are warmed up to 90 ℃ of insulation 12h, then obtain xerogel 100 ℃ of oven dry.It is transferred in the porcelain boat in tube type resistance furnace at Ar/H 2Under (Ar accounts for volume 3%), the speed with 5 ℃/min is heated to 400 ℃ of constant temperature 10, h first, speed with 5 ℃/min cools to room temperature again, and taking-up at compressing tablet, is calcined 24h with 650 ℃ temperature with powder again, naturally be down to room temperature, obtain oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite Li 2FeSiO 3.21N 0.48/ C.
The chemical property of gained sample is measured by the following method: the Li that weighing 0.75 gram oxygen-containing vacancy ferrosilicon silicate of lithium and carbon are compound 2FeSiO 3., 21N 0.48/ C active material, add 0.15g acetylene black as conductive agent, add again quality and be the aqueous solution of 10% isopropyl alcohol as the PTFE binding agent of solvent preparation, add the 2ml isopropyl alcohol as dispersant, after the sealing on star-like formula ball mill with the speed ball milling 4h of 500rpm, then get slurry and be pressed into thin slice with roll squeezer, the sequin that radius is 0.5cm is made in oven dry, claim to force together in nickel foam after its quality, make anodal disk.Take lithium metal as negative pole, with the LiPF of 1.0mol/L 6/ EC+DMC (1: 1) is electrolyte, and the celgard2300 thin slice is barrier film, is assembled into the CR2025 button cell in being full of the glove box of argon gas, at one night of ageing, carries out charge-discharge test.
Embodiment 4
With 1.16 gram FeCO 3With 2.08 gram Si (OC 2H 5) 4Mix, join in the absolute ethyl alcohol of 150ml, pH value is controlled at 9, behind the room temperature vigorous stirring 8h, adds 0.74 gram Li 2CO 3, 0.07 gram Li 3N and 0.2 gram glucose are warmed up to 90 ℃ of insulation 12h, then obtain xerogel 100 ℃ of oven dry.It is transferred in the porcelain boat in tube type resistance furnace at N 2/ H 2(H 2Account for volume 3%) under, the speed with 10 ℃/min is heated to 400 ℃ of constant temperature 12, h first, speed with 10 ℃/min cools to room temperature again, and taking-up at compressing tablet, is calcined 24h with 750 ℃ temperature with powder again, naturally be down to room temperature, obtain oxygen-containing vacancy ferrous metasilicate lithium/carbon composite material Li 2FeSiO 3.72N 0.18/ C.
The chemical property of gained sample is measured by the following method: the Li that weighing 0.75 gram oxygen-containing vacancy ferrosilicon silicate of lithium and carbon are compound 2FeSiO 3.72N 0.18/ C active material, add 0.15 gram acetylene black as conductive agent, add again quality and be the aqueous solution of 10% isopropyl alcohol as the PTFE binding agent of solvent preparation, add the 2ml isopropyl alcohol as dispersant, after the sealing on star-like formula ball mill with the speed ball milling 4h of 500rpm, then get slurry and be pressed into thin slice with roll squeezer, the sequin that radius is 0.5cm is made in oven dry, claim to force together in nickel foam after its quality, make anodal disk.Take lithium metal as negative pole, with the LiPF of 1.0mol/L 6/ EC+DMC (1: 1) is electrolyte, and the celgard2300 thin slice is barrier film, is assembled into the CR2025 button cell in being full of the glove box of argon gas, at one night of ageing, carries out charge-discharge test.
Embodiment 5
With 2.78 gram FeSO 47H 2O, and 2.08 gram Si (OC 2H 5) 4Mix, join in the absolute ethyl alcohol of 150ml, pH value is controlled at 9, behind the room temperature vigorous stirring 6h, adds 1.28g Li 2SO 4H 2O and 0.14 gram LiNO 3With 0.3 gram glucose, be warmed up to 80 ℃ of insulation 12h, then obtain xerogel 100 ℃ of oven dry.It is transferred in the porcelain boat in tube type resistance furnace under Ar, speed with 5 ℃/min is heated to 450 ℃ of constant temperature 12 first, h, speed with 5 ℃/min cools to room temperature again, taking-up with powder at compressing tablet, with 750 ℃ temperature calcining 24h, naturally be down to room temperature again, obtain oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite Li 2FeSiO 3.69N 0.17/ C.
The chemical property of gained sample is measured by the following method: the Li that weighing 0.75 gram oxygen-containing vacancy ferrosilicon silicate of lithium and carbon are compound 2FeSiO 3.69N 0.17/ C active material, add 0.15 gram acetylene black as conductive agent, add again quality and be the aqueous solution of 10% isopropyl alcohol as the PTFE binding agent of solvent preparation, add the 2ml isopropyl alcohol as dispersant, after the sealing on star-like formula ball mill with the speed ball milling 4h of 500rpm, then get slurry and be pressed into thin slice with roll squeezer, the sequin that radius is 0.5cm is made in oven dry, claim to force together in nickel foam after its quality, make anodal disk.Take lithium metal as negative pole, with the LiPF of 1.0mol/L 6/ EC+DMC (1: 1) is electrolyte, and the celgard2300 thin slice is barrier film, is assembled into the CR2025 button cell in being full of the glove box of argon gas, at one night of ageing, carries out charge-discharge test.
Embodiment 6
With 1.99 gram FeCl 24H 2O and 2.08 gram Si (OC 2H 5) 4Mix, join in the absolute ethyl alcohol of 150ml, pH value is controlled at 8.5, behind the room temperature vigorous stirring 6h, adds 0.84 gram LiCl and 0.3 gram glucose, is warmed up to 80 ℃ of insulation 12h, then obtains xerogel 120 ℃ of oven dry.It is transferred in the porcelain boat in tube type resistance furnace at N 2/ H 2(H 2Account for volume 3%) under, the speed with 10 ℃/min is heated to 400 ℃ of constant temperature 12, h first, speed with 5 ℃/min cools to room temperature again, and taking-up at compressing tablet, is calcined 24h with 750 ℃ temperature with powder again, naturally be down to room temperature, obtain oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite Li 2FeSiO 3.53N 0.30/ C.
The chemical property of gained sample is measured by the following method: the Li that weighing 0.75 gram oxygen-containing vacancy ferrosilicon silicate of lithium and carbon are compound 2FeSiO 3.53N 0.30/ C active material, add 0.15 gram acetylene black as conductive agent, add again quality and be the aqueous solution of 10% isopropyl alcohol as the PTFE binding agent of solvent preparation, add the 2ml isopropyl alcohol as dispersant, after the sealing on star-like formula ball mill with the speed ball milling 4h of 500rpm, then get slurry and be pressed into thin slice with roll squeezer, the sequin that radius is 0.5cm is made in oven dry, claim to force together in nickel foam after its quality, make anodal disk.Take lithium metal as negative pole, with the LiPF of 1.0mol/L 6/ EC+DMC (1: 1) is electrolyte, and the celgard2300 thin slice is barrier film, is assembled into the CR2025 button cell in being full of the glove box of argon gas, at one night of ageing, carries out charge-discharge test.
Embodiment 7
With 1.799 gram FeC 2O 42H 2O and 2.08 gram Si (OC 2H 5) 4Mix, join in the absolute ethyl alcohol of 150ml, pH value is controlled at 9, behind the room temperature vigorous stirring 10h, adds 2.04 gram LiAc2H 2O and 0.2 gram glucose are warmed up to 80 ℃ of insulation 12h, then obtain xerogel 100 ℃ of oven dry.It is transferred in the porcelain boat in tube type resistance furnace at Ar/NH 3((NH 3Account for volume 5%) under, the speed with 5 ℃/min is heated to 400 ℃ of constant temperature 12, h first, speed with 5 ℃/min cools to room temperature again, and taking-up at compressing tablet, is calcined 24h with 700 ℃ temperature with powder again, naturally be down to room temperature, obtain oxygen-containing vacancy ferrous metasilicate lithium/carbon composite material Li 2FeSiO 3.38N 0.39/ C.
The chemical property of gained sample is measured by the following method: the Li that weighing 0.75 gram oxygen-containing vacancy ferrosilicon silicate of lithium and carbon are compound 2FeSiO 3.38N 0.39/ C active material, add 0.15 gram acetylene black as conductive agent, add again quality and be the aqueous solution of 10% isopropyl alcohol as the PTFE binding agent of solvent preparation, add the 2ml isopropyl alcohol as dispersant, after the sealing on star-like formula ball mill with the speed ball milling 4h of 500rpm, then get slurry and be pressed into thin slice with roll squeezer, the sequin that radius is 0.5cm is made in oven dry, claim to force together in nickel foam after its quality, make anodal disk.Take lithium metal as negative pole, with the LiPF of 1.0mol/L 6/ EC+DMC (1: 1) is electrolyte, and the celgard2300 thin slice is barrier film, is assembled into the CR2025 button cell in being full of the glove box of argon gas, at one night of ageing, carries out charge-discharge test.
Embodiment 8
With 1.799 gram FeC 2O 42H 2O and 2.08 gram Si (OC 2H 5) 4Mix, join in the absolute ethyl alcohol of 150ml, pH value is controlled at 8, behind the room temperature vigorous stirring 6h, adds 2.04 gram LiAc2H 2O and 0.2 gram glucose are warmed up to 80 ℃ of insulation 12h, then obtain xerogel 100 ℃ of oven dry.It is transferred in the porcelain boat in tube type resistance furnace at Ar/H 2(H 2Accounting for volume 3%) under the atmosphere, the speed with 5 ℃/min is heated to 400 ℃ of constant temperature 12, h first, speed with 5 ℃/min cools to room temperature again, and taking-up at compressing tablet, is calcined 24h with 700 ℃ temperature with powder again, naturally be down to room temperature, obtain oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite Li 2FeSiO 4/ C.
The chemical property of gained sample is measured by the following method: the Li that weighing 0.75 gram oxygen-containing vacancy ferrosilicon silicate of lithium and carbon are compound 2FeSiO 4/ C active material, add 0.15 gram acetylene black as conductive agent, add again quality and be the aqueous solution of 10% isopropyl alcohol as the PTFE binding agent of solvent preparation, add the 2ml isopropyl alcohol as dispersant, after the sealing on star-like formula ball mill with the speed ball milling 4h of 500rpm, then get slurry and be pressed into thin slice with roll squeezer, the sequin that radius is 0.5cm is made in oven dry, claim to force together in nickel foam after its quality, make anodal disk.Take lithium metal as negative pole, with the LiPF of 1.0mol/L 6/ EC+DMC (1: 1) is electrolyte, and the celgard2300 thin slice is barrier film, is assembled into the CR2025 button cell in being full of the glove box of argon gas, at one night of ageing, carries out charge-discharge test.

Claims (9)

1. one kind based on serondary lithium battery oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite anode material, and its chemical expression is:
Li 2FeSiO 4-xN y/ C, 0＜x≤1,0＜y≤0.5 wherein, x, y are not 0 simultaneously, and the x 〉=3y/2 that satisfies condition.
2. the preparation method based on serondary lithium battery oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite anode material according to claim 1 is characterized in that may further comprise the steps:
1) with the divalence source of iron, the ratio 1:1 of amount of substance is pressed in the silicon source, fully be blended at least a solvent in water, absolute ethyl alcohol, the acetone with the liquid or solid of doping nitrogen source or gas, its gas nitrogenous source mixes by controlled atmospher control, regulates the pH value between 7-12, vigorous stirring 1-24h, carbon source with lithium source and reproducibility adds again, controls temperature at 70-160 ℃, vigorous stirring 1-48h, obtain front aggressiveness colloidal sol, aggressiveness xerogel before oven dry obtains under 60-150 ℃ temperature;
2) adopt the secondary high-temperature solid phase method, front aggressiveness xerogel speed with 1-20 ℃/min under inert atmosphere or reducing atmosphere is heated to 300-500 ℃ of constant temperature 1-24h, again with the cooling of the speed of 1-20 ℃/min or naturally cool to room temperature, with pressed powder, calcine 1-48h with 600-850 ℃ temperature again, after being cooled to room temperature, namely get oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite Li 2FeSiO 4-xN y/ C powder, wherein 0＜x≤1,0＜y≤0.5.
3. the preparation method based on serondary lithium battery oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite anode material according to claim 2 is characterized in that, described lithium source is lithium hydroxide, lithium acetate, lithium carbonate, lithium chloride, lithium sulfate or lithium nitrate.
4. the preparation method based on serondary lithium battery oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite anode material according to claim 2, it is characterized in that described divalence source of iron is ferrous oxalate, ferrous acetate, frerrous chloride, ferrous nitrate, ferrous carbonate, ferrous lactate or ferrous sulfate.
5. the preparation method based on serondary lithium battery oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite anode material according to claim 2 is characterized in that, described silicon source is methyl silicate or tetraethoxysilane.
6. the preparation method based on serondary lithium battery oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite anode material according to claim 2 is characterized in that, described carbon source is glucose, sucrose, acetylene black, carbon black or carbon gel, and its content is 5wt%-20wt%.
7. the preparation method based on serondary lithium battery oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite anode material according to claim 2, it is characterized in that described inert atmosphere or reducing atmosphere are nitrogen, ammonia, argon gas, nitrogen hydrogen mixeding gas, argon hydrogen mixture or carbon monoxide and carbon dioxide gas mixture.
8. the preparation method based on serondary lithium battery oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite anode material according to claim 2 is characterized in that, described pH value is regulated with lithium hydroxide, NaOH, potassium hydroxide or ammoniacal liquor.
9. the preparation method based on serondary lithium battery oxygen-containing vacancy ferrosilicon silicate of lithium and carbon composite anode material according to claim 2, it is characterized in that the nitrogenous source of described doping is lithium nitride, lithium nitrate, ethylenediamine, tetramethylethylenediamine, NEED, nitrogen or ammonia.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101582495A (en) * 2009-07-06 2009-11-18 中南大学 Anode composite material of lithium ion battery and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101582495A (en) * 2009-07-06 2009-11-18 中南大学 Anode composite material of lithium ion battery and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Benefits of N for O substitution in polyoxoanionic electrode materials: a first principles investigation of the electrochemical properties of Li2FeSiO4-yNy(y=0,0.5,1);M.Armand,et al;《J.Mater.Chem.》;20110307;第21卷;10026-10034 *
M.Armand,et al.Benefits of N for O substitution in polyoxoanionic electrode materials: a first principles investigation of the electrochemical properties of Li2FeSiO4-yNy(y=0,0.5,1).《J.Mater.Chem.》.2011,第21卷10026-10034.

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