CN104157853A - Negative electrode material and preparation method and application of negative electrode material - Google Patents
Negative electrode material and preparation method and application of negative electrode material Download PDFInfo
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- CN104157853A CN104157853A CN201410362731.0A CN201410362731A CN104157853A CN 104157853 A CN104157853 A CN 104157853A CN 201410362731 A CN201410362731 A CN 201410362731A CN 104157853 A CN104157853 A CN 104157853A
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The invention discloses a negative electrode material which comprises zinc oxide particles coated with carbon layers and zinc ferrite particles coated with carbon layers, wherein the particle sizes of the zinc oxide particles and the zinc ferrite particles are smaller than 5nm; the carbon layers are 1 to 2nm thick; the zinc oxide particles coated with the carbon layers and the zinc ferrite particles coated with the carbon layers are stacked to form composite micro particles; the weight ratio of the zinc oxide particles to the zinc ferrite particles in the composite micro particles is (0.35-0.4) to 1; the particle sizes of the composite micro particles are 100 to 300nm; pores are formed between the zinc oxide particles coated with the carbon layers and the zinc ferrite particles coated with the carbon layer. The carbon-coated zinc-based composite oxide hollow octagonal negative electrode material is high in specific capacity, high in rate capability and high in cycle stability.
Description
Technical field
The present invention relates to lithium ion battery field, be specifically related to a kind of negative material, its preparation method and application.
Background technology
Lithium ion battery has had the advantages such as high-energy-density, high working voltage, memory-less effect and is used widely since commercialization due to it.But along with the increase of the demand to the extensive energy storage device storing for novel energy, the energy density of traditional commercial Li-ion batteries and power density can not satisfy the demands, exploitation has high power capacity, powerful battery material is extremely urgent.Current commercial Li-ion batteries negative material adopts the graphite material that specific capacity is 372mAh/g, although it has good cycle performance, but its specific capacity is lower, and under high current charge-discharge condition, easily produce potential safety hazard, limited its application in extensive energy storage field.
Zinc-base ternary compound oxides is because it has high power capacity, lower-price characteristic is widely studied.But it is subject to storing up the restriction that has volumetric expansion in lithium process, it is compound that researcher often adopts carbon-based material to carry out with it, and complex method is conventionally comparatively complicated, can not meet the requirement that large-scale industrialization is produced.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, the button cell that a kind of preparation method of loose structure negative material, the electrode slice that contains this negative material is provided and contains this electrode slice, solves the problem that current negative material finite capacity, high rate performance are low, can not carry out on a large scale suitability for industrialized production.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of negative material, comprise the zinc ferrite particle that is coated with the Zinc oxide particles of carbon-coating and is coated with carbon-coating, the granularity of Zinc oxide particles and zinc ferrite particle is all less than 5nm, the thickness of carbon-coating is 1～2nm, be coated with the Zinc oxide particles of carbon-coating and be coated with carbon-coating zinc ferrite particle packing form composite particles, in described composite particles, the weight ratio of Zinc oxide particles and zinc ferrite particle is 0.35～0.4:1, the granularity of composite particles is 100～300nm, is coated with the Zinc oxide particles of carbon-coating and is coated with between the zinc ferrite particle of carbon-coating to form hole.
A preparation method for the coated hollow octahedra negative material of zinc-base compound oxide of carbon of loose structure, comprises the following steps:
1) preparation reaction precursor liquid: A component is dissolved in and makes reaction precursor liquid in B component; Wherein A component comprises following raw material by ratio of weight and the number of copies: 63～64 parts of the polyvinylpyrrolidones that 14～15 parts of zinc nitrates, 18～20 parts of ferric acetyl acetonades, 2～3 parts of terephthalic acid (TPA)s, molecular weight are 30000～60000; B component is the N preparing for 4:3～2:1 by volume, the mixed liquor of N – dimethyl formamide and ethanol; In the reaction precursor liquid of preparation, nitric acid zinc concentration is 3.43～3.53g/L;
2) by step 1) preparation reaction precursor liquid at 95～105 DEG C, reflux 3～24 hours, product is used respectively to N, after N – dimethyl formamide and ethanol cyclic washing, in 60～120 DEG C of oven dry, obtain having the metal organic frame material of hollow octahedral structure;
3) the metal organic frame material after drying is risen to 500～600 DEG C with the heating rate of 0.5～3 DEG C/min in nitrogen atmosphere, naturally cool to immediately room temperature and can obtain negative material, it is Powdered drying the product obtaining.
A kind of electrode slice, comprises following raw material by ratio of weight and the number of copies:
40～80 parts of negative materials; 10～40 parts of conductive blacks; 10～20 parts of Lithium polyacrylate binding agents.
A kind of button cell, comprises above-mentioned electrode slice.
The invention has the beneficial effects as follows:
1. the negative material specific capacity of preparing is high, good rate capability;
2. the negative material good cycling stability of preparing, coulomb efficiency is high first;
3. the negative material of preparing has loose structure, and metal oxide surface carbon coating layer is even and be interconnected to form 3D network, has improved electrical conductivity performance and the ionic conduction performance of active material, has suppressed bulk effect;
4. preparation method is simple, is applicable to large-scale production.
Brief description of the drawings
In Fig. 1, (a), (b) be respectively that field emission scanning electron microscope (FSEM) figure and the transmission electron microscope (TEM) of synthetic metal organic frame material (MOF) schemed.(c), (d) be respectively FSEM figure and the TEM figure of the coated hollow octahedra negative material of zinc-base compound oxide of the carbon that obtains after heat treatment in 500 DEG C of nitrogen of metal organic frame material (MOF), (e), (f) be that constituency high resolution transmission electron microscopy (HRTEM) is schemed;
Fig. 2 is X-ray diffraction (XRD) collection of illustrative plates of the coated hollow octahedra negative material of zinc-base compound oxide of carbon;
Fig. 3 (a), (b) are respectively nitrogen adsorption desorption curve and the graph of pore diameter distribution of the coated hollow octahedra negative material of zinc-base compound oxide of carbon;
Fig. 4 is the cyclic voltammetry curve of the coated hollow octahedra negative material of zinc-base compound oxide of carbon, test specification 3-0.005V, sweep speed 0.2mV/s;
Fig. 5 is that the coated hollow octahedra negative material of zinc-base compound oxide of carbon is the charging and discharging curve figure under 0.5A/g in current density;
Fig. 6 is the cycle performance figure of the coated hollow octahedra negative material of zinc-base compound oxide of carbon under current density 0.5A/g and 2A/g current density;
Fig. 7 is high rate performance and the cycle performance figure of the electrode slice that contains the coated hollow octahedra negative material of zinc-base compound oxide of carbon.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.In addition,, in each execution mode of described the present invention, involved technical characterictic just can combine mutually as long as do not form each other conflict.
Embodiment mono-
The first step, preparation reaction precursor liquid: A component is dissolved in and makes reaction precursor liquid in B component; Wherein A component comprises following raw material by ratio of weight and the number of copies: 14～15 parts of zinc nitrates, 18～20 parts of ferric acetyl acetonades, 2～3 parts of terephthalic acid (TPA)s, molecular weight are 63～64 parts of 30000～60000 polyvinylpyrrolidones; B component is the N preparing for 4:3～2:1 by volume, the mixed liquor of N – dimethyl formamide and ethanol; In the reaction precursor liquid being mixed with, nitric acid zinc concentration is 3.43～3.53g/L.
As above-mentioned number range preferably, the ratio of weight and number of each raw material of A component is respectively: zinc nitrate can be that 14.6～14.7 parts, ferric acetyl acetonade are that 18.9～19.1 parts, terephthalic acid (TPA) are that 2.9～3.1 parts, polyvinylpyrrolidone are 63～63.5 parts.
The further preferred N of the present embodiment, the volume 300mL of N – dimethyl formamide (DMF), the volume 180mL of ethanol, after the two is mixed, the polyvinylpyrrolidone (PVP) that is 55000 to the molecular weight that adds 1.67 grams of zinc nitrates, 2.16 grams of ferric acetyl acetonades, 0.34 gram of terephthalic acid (TPA) and 7.2 grams in mixed liquor again, stirs and forms orange-red reaction precursor liquid (polyvinylpyrrolidone, ferric acetyl acetonade, zinc nitrate and the terephthalic acid (TPA) that add are solid).In the reaction precursor liquid of preparation, the concentration of PVP is about 15g/L, and nitric acid zinc concentration is about 3.48g/L, and the concentration of ferric acetyl acetonade is about 4.5g/L, and the concentration of terephthalic acid (TPA) is about 0.71g/L.
Second step refluxes reaction precursor liquid 3～24 hours at 95～105 DEG C, and product is used respectively to N, after N – dimethyl formamide and ethanol cyclic washing, in 60～120 DEG C of oven dry, obtains having the metal organic frame material of hollow octahedral structure.
As above-mentioned number range preferably, reaction precursor liquid can be refluxed 4～8 hours at 99～101 DEG C, use respectively N, after the each washing of N – dimethyl formamide and ethanol 2～4 times in 60～120 DEG C of oven dry.
The present embodiment further preferably refluxes reaction precursor liquid 6 hours at 100 DEG C, by the product centrifugation obtaining, then is placed on 80 DEG C of oven dry for 3 times with the each washing of DMF and ethanol.
The 3rd step, is placed in tube furnace by the metal organic frame material after drying, and in nitrogen atmosphere, rises to 500～600 DEG C with the heating rate of 0.5～3 DEG C/min.
As above-mentioned number range preferably, can in nitrogen atmosphere, be raised to 500～550 DEG C with the heating rate of 0.5～1.5 DEG C/min.
The present embodiment further preferably rises to 500 DEG C with the heating rate of 1 DEG C/min under nitrogen atmosphere, without insulation, directly naturally cools to room temperature, can obtain the coated hollow octahedra negative material of zinc-base compound oxide of carbon.
This negative material comprises the zinc ferrite particle that is coated with the Zinc oxide particles of carbon-coating and is coated with carbon-coating, the granularity of Zinc oxide particles and zinc ferrite particle is all less than 5nm, the thickness of carbon-coating is 1～2nm, be coated with the Zinc oxide particles of carbon-coating and be coated with carbon-coating zinc ferrite particle packing form composite particles, in described composite particles, the weight ratio of Zinc oxide particles and zinc ferrite particle is 0.35～0.4:1, the granularity of composite particles is 100～300nm, is coated with the Zinc oxide particles of carbon-coating and is coated with between the zinc ferrite particle of carbon-coating to form hole.
Composite particles be shaped as hollow octahedral structure, after being coated with the Zinc oxide particles of carbon-coating and being coated with the zinc ferrite particle packing of carbon-coating, between particle, form a lot of holes, making octahedral structure is loose structure.
The coated hollow octahedra negative material of zinc-base compound oxide of the carbon with loose structure of preparing by said method has remarkable storage lithium performance, is a kind of desirable negative material.
Fig. 1 (a) is the FSEM figure of the metal organic frame material (MOF) that obtains, from figure, can observe clearly its octahedral structure for particle diameter 200nm left and right, can find out that from TEM figure (Fig. 1 (b)) it has obvious hollow-core construction.And in Fig. 1 (c) and Fig. 1 (d), can confirm that metal organic frame material (MOF) still can keep initial octahedral structure after Overheating Treatment.Can see clearly at the grain edges of the metal oxide one deck that distributing equably and be about the carbon-coating of about 1nm by the high-resolution TEM figure of Fig. 1 (e).Fig. 1 (f) shows that metal oxide particle size is less than 5nm.
In Fig. 2, be the XRD figure of the coated hollow octahedra negative material of zinc-base compound oxide of carbon, determine that this sample is to be mainly made up of zinc oxide and two kinds of components of zinc ferrite.
The specific area that can calculate the coated hollow octahedra negative material of zinc-base compound oxide of carbon from the adsorption desorption curve of Fig. 3 is about 140m
2/ g, the pore size of formation differs, and the size of hole is mainly distributed in 7.5nm left and right.
The coated carbon obtained above hollow octahedra negative material of zinc-base compound oxide is mixed by the weight ratio of 70:15:15 with conductive black, Lithium polyacrylate binding agent, and process is colded pressing, the die-cut electrode slice of making.Using metal lithium sheet as to electrode, with the LiPF of 1mol/L
6/ EC+DMC is electrolyte, and charging/discharging voltage scope is 3.0～0.001V.
Fig. 4 is the cyclic voltammetry curve figure of the electrode slice that contains the coated hollow octahedra negative material of zinc-base compound oxide of carbon.In negative electrode scanning process first, be that an obvious reduction peak in place appears in 0.75V place at voltage, it corresponds to the decomposition of the decomposition of electrolyte and the formation of SEI film and zinc oxide and zinc ferrite.The reduction peak occurring at 0.2V place subsequently corresponds to the alloy reaction of Li-Zn.In anode scanning process subsequently, the oxidation peak at 1.6V place corresponds to the oxidation reaction of Zn and Fe.From second week scanning, the reduction peak of first circle 0.75V is moved to 0.87V, and all the other peak positions and intensity are almost constant, has embodied the electrochemical reaction of this material in storage lithium process and has had height invertibity.
Fig. 5 is that the coated hollow octahedra negative material of zinc-base compound oxide of carbon is the charging and discharging curve figure under 0.5A/g in current density.Can find out from the curve of Fig. 5, in discharge process first, can observe a discharge platform at 0.75V place, correspond to ZnFe
2o
4be decomposed into Zn, Fe and Li
2o, its first charge-discharge capacity is respectively 1047 and 1385mAh/g, and coulomb efficiency is up to 75.6%.
The cycle performance figure of the electrode slice that Fig. 6 contains the coated hollow octahedra negative material of zinc-base compound oxide of carbon under the electric current of 500mA/g and 2A/g, after 100 put-charging cycle of experience, capacity still can keep 1390mAh/g and 988mAh/g.Meanwhile, it still shows storage lithium ability free from worldly cares under high current density.
As shown in Figure 7, it still has the reversible capacity up to 762mAh/g under the condition of current density 10A/g (completing charging process in 5 minutes), embodies outstanding high rate performance.
Below in conjunction with a comparative example, the sample obtaining in comparative example and the effect of the coated hollow octahedra negative material of zinc-base compound oxide of the carbon that utilizes the method for the embodiment of the present invention one to prepare are contrasted.
Comparative example:
Comparative example is that metal organic frame material (MOF) that the first two steps of embodiment mono-are obtained heat-treats with same program in air atmosphere that (1 DEG C/min of programming rate rises to 500 DEG C, naturally cool to room temperature), obtain the hollow octahedra negative material of zinc-base compound oxide that does not have carbon coated.The negative material of comparative example gained is assembled into button cell by the mode identical with embodiment mono-, test electrical property.
Table 1 is the button cell electrical property contrast with comparative example negative material containing embodiment mono-
In sum, the coated hollow octahedra negative material of zinc-base compound oxide of carbon that the preparation method who proposes according to the present invention prepares has good capacity and cycle performance, and preparation method is simple, is applicable to large-scale production.
It should be noted that, the announcement of book and elaboration according to the above description, those skilled in the art in the invention can also change and revise above-mentioned execution mode.Therefore, the present invention is not limited to embodiment disclosed and described above, also should be in the protection range of claim of the present invention to equivalent modifications more of the present invention and change.In addition,, although used some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (4)
1. a negative material, it is characterized in that: comprise the zinc ferrite particle that is coated with the Zinc oxide particles of carbon-coating and is coated with carbon-coating, the granularity of Zinc oxide particles and zinc ferrite particle is all less than 5nm, the thickness of carbon-coating is 1～2nm, be coated with the Zinc oxide particles of carbon-coating and be coated with carbon-coating zinc ferrite particle packing form composite particles, in described composite particles, the weight ratio of Zinc oxide particles and zinc ferrite particle is 0.35～0.4:1, the granularity of composite particles is 100～300nm, be coated with the Zinc oxide particles of carbon-coating and be coated with between the zinc ferrite particle of carbon-coating and form hole.
2. a method of preparing negative material described in claim 1, is characterized in that: comprise the following steps:
1) preparation reaction precursor liquid: A component is dissolved in and makes reaction precursor liquid in B component; Wherein A component comprises following raw material by ratio of weight and the number of copies: 63～64 parts of the polyvinylpyrrolidones that 14～15 parts of zinc nitrates, 18～20 parts of ferric acetyl acetonades, 2～3 parts of terephthalic acid (TPA)s, molecular weight are 30000～60000; B component is the N preparing for 4:3～2:1 by volume, the mixed liquor of N – dimethyl formamide and ethanol; In the reaction precursor liquid of preparation, nitric acid zinc concentration is 3.43～3.53g/L;
2) by step 1) preparation reaction precursor liquid at 95～105 DEG C, reflux 3～24 hours, product is used respectively to N, after N – dimethyl formamide and ethanol cyclic washing, in 60～120 DEG C of oven dry, obtain having the metal organic frame material of hollow octahedral structure;
3) the metal organic frame material after drying is risen to 500～600 DEG C with the heating rate of 0.5～3 DEG C/min in nitrogen atmosphere, naturally cool to immediately room temperature.
3. an electrode slice, is characterized in that: comprise by ratio of weight and the number of copies following raw material:
40～80 parts of negative materials claimed in claim 1; 10～40 parts of conductive blacks; 10～20 parts of Lithium polyacrylate binding agents.
4. a button cell, is characterized in that: comprise electrode slice claimed in claim 3.
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| CN107364897A (en) * | 2017-08-17 | 2017-11-21 | 大连理工大学 | A kind of preparation method of ferrous acid zinc nano material |
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| CN106975489A (en) * | 2017-04-26 | 2017-07-25 | 浙江大学 | A kind of preparation method of nickel oxide in-stiu coating graphene nanocomposite material |
| CN106975489B (en) * | 2017-04-26 | 2019-12-31 | 浙江大学 | Preparation method of nickel oxide in-situ coated graphene nanocomposite |
| CN107611363A (en) * | 2017-07-26 | 2018-01-19 | 华南理工大学 | A kind of fusiform cobalt ferrite/carbon lithium ion cell nano composite negative pole material and preparation method and application |
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| CN107611361A (en) * | 2017-07-26 | 2018-01-19 | 华南理工大学 | A kind of fusiform structure ferrous acid nickel carbon lithium ion cell nano composite negative pole material and preparation method and application |
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