CN102651472A - Composite cathode material of lithium ion battery and preparation method thereof - Google Patents
Composite cathode material of lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a composite cathode material of a lithium ion battery and a preparation method thereof, and mainly aims to improve the electrical chemical performance of the composite cathode material of the lithium ion battery. The composite cathode material of the lithium ion battery is a composite material formed by ZnO and FeO, or the composite material formed by coating ZnO and FeO by porous carbon C. The preparation method comprises the steps of: mixing to obtain a ferrite-zinc mixed solution, adding an organic pyrolytic carbon precursor into the ferrite-zinc mixed solution, preserving heat and solidifying, and sintering at a constant temperature. Compared with the prior art, by adopting the invention, the excellent de-lithium-intercalation ability, higher specific capacity and excellent cycling stability of transition metal oxide can be kept; the first reversible specific capacity is more than 700mAh/g, and the reversible specific capacity is more than 400mAh/g after cycling for 80 weeks; the composite cathode material is simple in manufacturing method, low in cost, little in environment pollution, and applicable to the cathode material of the lithium ion battery for lithium ion storage batteries, power batteries, various portable device, electrical tools and the like.
Description
Technical field
The present invention relates to a kind of cell negative electrode material and preparation method thereof, particularly a kind of lithium ion battery cathode material and its preparation method.
Background technology
Since Gaston Plante in 1859 proposed the notion of lead-acid battery, chemical power source circle attempted to develop the height ratio capacity that makes new advances, the secondary cell of long circulation life always.Lithium ion battery formally comes into operation whole 20 years as a kind of new-type secondary battery; It has that voltage height (4V), energy density are high, self discharge is little, have extended cycle life, memory-less effect, pollution-free advantage, has been widely used on the movable equipments such as notebook computer, mobile phone, digital camera and electric motor car at present.
Commercially available lithium ion battery mainly adopts the graphite-like material with carbon element as negative material at present, and graphite material has following shortcoming: 1, theoretical specific capacity is merely 372mAh/g, and actual capacity is lower; 2, have height-oriented layer structure, very poor with the compatibility of organic electrolyte: as 3, to exist graphite linings to peel off phenomenon in the fast charging and discharging process, cause capacity attenuation; 4, its embedding lithium current potential is easy to generate the Li dendrite phenomenon very near the lithium deposition potential, causes potential safety hazard.Therefore, it is big further to improve the performance difficulty of graphite type material.In order to satisfy the demand of people, must develop the high performance negative material of high power capacity of new generation to high-capacity battery.The high power capacity negative material mainly concentrates on two big types at present: one type of simple substance material and oxide thereof for Si and Sn, or its composite material, another kind of is metal oxide.The storage lithium mechanism of said metal oxide roughly can be divided into two kinds: 1, alloy-type mechanism, and like ZnO+Li → Zn+Li
2O, Zn+Li ← → LiZn; 2, oxidation-reduction type mechanism, as FeO+Li ← → Fe+Li
2O.Metal oxide based on these two kinds of mechanism shows the gram volume that doubles graphite, but has some shortcomings: this metal oxide itself is the very poor semi-conducting material of a kind of conductivity, and the Li that generates in the reaction
2O has worsened conductivity more; The reaction of metal oxide and Li produces " volumetric expansion effect "; Electrode " efflorescence " can appear in removal lithium embedded repeatedly; Not only lose and electrically contact with collector; The forfeiture electro-chemical activity finally causes cycle performance to descend but also " reunion " takes place the metallic particles that can make generation, has limited the application of this metal oxide in lithium ion battery.
Summary of the invention
The purpose of this invention is to provide a kind of composite cathode material for lithium ion cell and preparation method thereof, the technical problem that solve is to improve the chemical property of transition metal oxide composite negative pole material.
The present invention adopts following technical scheme: a kind of composite cathode material for lithium ion cell; Said composite cathode material for lithium ion cell is the ZnO/FeO composite material that ZnO and FeO form; ZnO is 1 ~ 24:8 with the ratio of the amount of substance of FeO, or the ZnO/FeO/C composite material of porous carbon C clading ZnO and FeO formation, and C is 1 ~ 14:4 with the ratio of the amount of substance of ZnO, FeO sum; The average grain diameter of ZnO/FeO composite material and ZnO/FeO/C composite material is 10 ~ 60 μ m, and specific area is 1 ~ 20m
2/ g.
A kind of preparation method of composite cathode material for lithium ion cell; May further comprise the steps: one, with zinc nitrate, zinc chloride or zinc acetate zinc solution and ferric nitrate, iron chloride or ironic citrate iron salt solutions; Press the ratio 1 ~ 24:8 of zinc salt and molysite amount of substance, mix obtaining iron zinc mixed solution; Two, the organic matter pyrolysis carbon matrix precursor is added in the iron zinc mixed solution, temperature is 50 ~ 100 ℃, and rotating speed is 10 ~ 25r/min, stirs 30 ~ 180min, obtains even slurry; Said organic matter pyrolysis carbon matrix precursor is more than one in citric acid, glucose, phenolic resins, epoxy resin and the sucrose; The organic matter pyrolysis carbon matrix precursor is pressed the ratio of carbon atom and the amount of zinc-iron atom species; Be (0＜carbon atom amount of substance≤1): (amounts of 4 zinc-iron atom species), or (amount of 1＜carbon atom amount of substance≤14:4 zinc-iron atom species); Three, even slurry is warming up to 50 ~ 200 ℃ with 0.5 ~ 3 ℃/min heating rate from room temperature, heat preservation solidification 5 ~ 48h naturally cools to room temperature in the stove; Four, at protective atmosphere nitrogen or argon gas; Flow is under 0.9 ~ 2L/min condition, is warming up to 700 ~ 900 ℃ with 0.5 ~ 5 ℃/min heating rate from room temperature, constant temperature sintering 14 ~ 24h; Naturally cool to room temperature in the stove; Obtaining composite cathode material for lithium ion cell, is the ZnO/FeO composite material of ZnO and FeO formation, or the ZnO/FeO/C composite material of porous carbon C clading ZnO and FeO formation.
Constant temperature sintering 14 ~ 24h of the present invention, naturally cool to room temperature in the stove after, put into planetary ball mill; Ball milling 2 ~ 10h, ball material mass ratio is 10 ~ 20:1, ball material is a stainless shot; Diameter is 10mm, and sieving through 200 orders obtains the composite cathode material for lithium ion cell that average grain diameter is 10 ~ 60 μ m.
The present invention is that 0.1 ~ 10mol/L is dissolved in the deionized water with zinc nitrate, zinc chloride or zinc acetate by zinc atom concentration, obtains zinc solution; Is that 0.1 ~ 10mol/L is dissolved in the deionized water with ferric nitrate, iron chloride or ironic citrate by iron atom concentration, obtains iron salt solutions.
The present invention is that 0.1 ~ 10mol/L is dissolved in the deionized water with zinc nitrate, zinc chloride or zinc acetate by zinc atom concentration, and temperature is 25 ~ 50 ℃, and rotating speed is 10 ~ 25r/min, and the time is 30 ~ 180min; Said is that 0.1 ~ 10mol/L is dissolved in the deionized water with ferric nitrate, iron chloride or ironic citrate by iron atom concentration, and temperature is 25 ~ 50 ℃, and rotating speed is 10 ~ 25r/min, and the time is 30 ~ 180min.
Of the present invention with zinc solution and iron salt solutions, be 10 ~ 50 ℃ in temperature, rotating speed is 10 ~ 25r/min, the time is to mix under 30 ~ 180min condition to obtain iron zinc mixed solution.
When organic matter pyrolysis carbon matrix precursor of the present invention was two or more, every kind of material added respectively, was under 10 ~ 25r/min at rotating speed respectively, stirred 30 ~ 180min.
Step 1 of the present invention is pressed the ratio 1.6 ~ 8:8 of zinc salt and molysite amount of substance; Said step 2, temperature are 70 ~ 100 ℃, and rotating speed is 10 ~ 15r/min; Stir 30 ~ 120min; The organic matter pyrolysis carbon matrix precursor is pressed the ratio of carbon atom and the amount of zinc-iron atom species, is 0.08＜carbon atom amount of substance≤0.96:4, or 2.12＜carbon atom amount of substance≤13.44:4; Said step 3 is warming up to 100 ~ 150 ℃ with 1 ~ 3 ℃/min heating rate from room temperature, heat preservation solidification 5 ~ 24h; Said step 4, flow are 0.9 ~ 1.5L/min, are warming up to 700 ~ 750 ℃ with 0.5 ~ 4 ℃/min heating rate from room temperature.
Step 1 of the present invention is pressed the ratio 4:8 of zinc salt and molysite amount of substance; Said step 2, temperature are 90 ℃, and rotating speed is 15r/min, stir 90min, and the organic matter pyrolysis carbon matrix precursor is pressed the ratio of carbon atom and the amount of zinc-iron atom species, is 0.8:4, or 9.92:4; Said step 3 is warming up to 110 ℃ with 2 ℃/min heating rate from room temperature, heat preservation solidification 12h; Said step 4, flow are 1L/min, are warming up to 700 ℃ with 3 ℃/min heating rate from room temperature, constant temperature sintering 24h.
The present invention through the composite negative pole material of preparation transition metal oxide, and is under the micron-sized situation at particle diameter compared with prior art, can keep the good removal lithium embedded ability of transition metal oxide; Higher specific capacity and cyclical stability preferably, reversible specific capacity is greater than 700mAh/g first, and 80 weeks of circulating remain on more than the 400mAh/g, through mixing; Heat treatment, grinding steps, manufacture method is simple, and cost is low; Environmental pollution is little, is applicable to lithium-ion energy storage battery, electrokinetic cell; Various portable device, electric tool etc. are used lithium ion battery negative material, have good industrial prospect.
Description of drawings
Fig. 1 is the SEM picture of the ZnO/FeO/C composite negative pole material of embodiment 1.
Fig. 2 is the XRD figure spectrum of the ZnO/FeO/C composite negative pole material of embodiment 1.
Fig. 3 is the charging and discharging curve of the ZnO/FeO/C composite negative pole material of embodiment 1.
Fig. 4 is the cycle performance curve of the ZnO/FeO/C composite negative pole material of embodiment 1.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done further explain.Composite cathode material for lithium ion cell of the present invention; ZnO/FeO composite material for ZnO and FeO formation; ZnO is 1 ~ 24:8 with the ratio of the amount of substance of FeO, or the ZnO/FeO/C composite material of porous carbon C clading ZnO and FeO formation, and C is 1 ~ 14:4 with the ratio of the amount of substance of ZnO, FeO sum; The average grain diameter of ZnO/FeO composite material and ZnO/FeO/C composite material is 10 ~ 60 μ m, and specific area is 1 ~ 20m2/g.
The preparation method of composite cathode material for lithium ion cell of the present invention may further comprise the steps:
One, be that 0.1 ~ 10mol/L is dissolved in the deionized water with zinc salt by zinc atom concentration, magnetic agitation, temperature are 25 ~ 50 ℃, and rotating speed is 10 ~ 25r/min, and the time is 30 ~ 180min, dissolve fully to zinc salt, obtain zinc solution.Is that 0.1 ~ 10mol/L is dissolved in the deionized water with molysite by iron atom concentration, and magnetic agitation, temperature are 25 ~ 50 ℃, and rotating speed is 10 ~ 25r/min, and the time is 30 ~ 180min, dissolves fully to molysite, obtains iron salt solutions.
Zinc salt is zinc nitrate, zinc chloride or zinc acetate.
Molysite is ferric nitrate, iron chloride or ironic citrate.
Two, with zinc solution and iron salt solutions, press the ratio 1 ~ 24:8 of zinc salt and molysite amount of substance, be 10 ~ 50 ℃ in temperature, rotating speed is 10 ~ 25r/min, the time is that 30 ~ 180min condition lower magnetic force mixes, and obtains iron zinc mixed solution.
Three, the organic matter pyrolysis carbon matrix precursor is added in the iron zinc mixed solution, temperature is 50 ~ 100 ℃, and rotating speed is 10 ~ 25r/min, and constant temperature magnetic agitation 30 ~ 180min obtains even slurry.
The organic matter pyrolysis carbon matrix precursor is more than one in citric acid, glucose, phenolic resins, epoxy resin and the sucrose.When the organic matter pyrolysis carbon matrix precursor that adds when being two or more, every kind of material can add respectively under same temperature, is under 10 ~ 25r/min at rotating speed respectively, constant temperature magnetic agitation 30 ~ 180min.
The organic matter pyrolysis carbon matrix precursor is pressed the ratio of carbon atom and the amount of zinc-iron atom species, when (0＜carbon atom amount of substance≤1): when (amounts of 4 zinc-iron atom species), obtain the ZnO/FeO composite material that ZnO and FeO form behind the sintering; When (amount of 1＜carbon atom amount of substance≤14:4 zinc-iron atom species), obtain the ZnO/FeO/C composite material that porous carbon C clading ZnO and FeO form behind the sintering.Because the carbon amount more after a little while, all carbon is participated in ferric reduction reaction and is generated CO
2Gas is excluded, and noresidue carbon exists; The carbon amount more for a long time, only part carbon is participated in ferric reduction reaction and is excluded, and has residual carbon to exist.
Four, even slurry is moved in the baking oven, be warming up to 50 ~ 200 ℃ with 0.5 ~ 3 ℃/min heating rate from room temperature (20 ℃), heat preservation solidification 5 ~ 48h makes slurry become xerogel, naturally cools to room temperature in the stove.
Five, cooled material is put into planetary ball mill, ball milling 2 ~ 10h, ball material mass ratio is 10 ~ 20:1; Ball material is a stainless shot; Diameter is 10mm, obtains the powder that average grain diameter is 10 ~ 200 μ m, powder is moved in the batch (-type) rotary furnace of SHFB96/16 type Muffle furnace or Japanese high sand Industrial Co., Ltd of sigma (Shanghai) high-temperature electric resistance furnace Co., Ltd again; Under protective atmosphere; Be warming up to 700 ~ 900 ℃ with 0.5 ~ 5 ℃/min heating rate from room temperature (20 ℃), constant temperature sintering 14 ~ 24h naturally cools to room temperature in the stove.
Protective gas is nitrogen or argon gas, and flow is 0.9 ~ 2L/min.
Six, put into planetary ball mill once more after the cooling; Ball milling 2 ~ 10h, ball material mass ratio is 10 ~ 20:1, ball material is a stainless shot; Diameter is 10mm; Last powder sieves through 200 orders and obtains the composite cathode material for lithium ion cell that average grain diameter is 10 ~ 60 μ m, and composite cathode material for lithium ion cell is the ZnO/FeO composite material that ZnO and FeO form, or the ZnO/FeO/C composite material of porous carbon C clading ZnO and FeO formation.
The composite material ZnO/FeO of the inventive method preparation is based on two kinds of metal oxides; The storage lithium characteristic of two kinds of metal oxides comes from alloy-type mechanism and oxidation-reduction type mechanism respectively; Though all there is the volumetric expansion phenomenon in the process at removal lithium embedded, both coefficients of cubical expansion are different with the elasticity factor, all can be used as the other side's volume buffer; Make electrode material be difficult for efflorescence, optimized the cycle performance of single metal oxide to a certain extent.Another composite material ZnO/FeO/C that the inventive method obtains is based on porous carbon clading ZnO and FeO, and itself has high conductivity material with carbon element, so carbon coats the conductivity that has improved metal oxide, can make active material participate in electrode reaction faster; On the other hand, porous carbon is present between two kinds of metal oxides as the long-pending expansion cushion space of two-phase mixture, has suppressed the efflorescence of electrode material and the reunion of active material, has increased cyclical stability greatly.
The composite cathode material for lithium ion cell of the inventive method preparation; With Japanese Hitachi-S4800 scanning electronic microscope observation composite material surface pattern; Measure its composition, structure with Dutch Panalytical X ' pert PRO X-ray diffraction analysis appearance; Measure its particle diameter with Britain Malvern Mastersizer 2000 laser particle size analyzers, with the BET method of nitrogen adsorption, U.S. health tower Nova 1000e specific area/its specific area of aperture analysis-e/or determining.
With the composite cathode material for lithium ion cell that the inventive method prepares, make the active material of lithium ion battery negative material, carbon black Super P is a conductive agent, Kynoar PVDF is that binding agent makes electrode material.The three according to the proportioning of quality is: active material: conductive agent: binding agent=8:1:1; Adopt paste mixer to mix well into pasty state to wherein adding an amount of N-methyl pyrrolidone (NMP); Adopt coating machine coating then on Copper Foil; Coating thickness is 200 μ m, and it is the pole piece of 8.4mm that oven dry back punching becomes diameter.With pour lithium slice is to electrode, and this pole piece is a work electrode, and (anodal stainless steel gasket diameter is 8.4mm to adopt Celgard 2400 barrier films in German Braun glove box, to be assembled into die type; Negative pole copper backing diameter is 11.4mm) simulated battery.Electrolyte adopts the solution of 1M LiPF6/EC+DMC, and wherein ethylene carbonate EC and dimethyl carbonate DMC volume ratio are 1:1.With Wuhan gold promise Land CT 2001A charge-discharge test cabinet, in the voltage range of 0.001 ~ 3V, carry out the test of simulated battery charge-discharge performance with the current density of 100mA/g.
Embodiment 1
One, takes by weighing 74.37g (0.25mol) Zn (NO
3)
26H
2O is dissolved in the 300ml deionized water, 25 ℃ of temperature, and rotating speed 10r/min, magnetic agitation 180min obtains the zinc solution that zinc atom concentration is 0.83mol/L.Take by weighing 202g (0.5mol) Fe (NO again
3)
3.9H
2O is dissolved in another 300ml deionized water, 25 ℃ of temperature, and rotating speed 10r/min, magnetic agitation 180min obtains the iron salt solutions that iron atom concentration is 1.67mol/L.
Two, zinc solution is mixed with iron salt solutions, zinc salt and molysite mol ratio are 1:2,25 ℃ of temperature, and rotating speed 10r/min, magnetic agitation 180min obtains iron zinc mixed solution.
Three, in iron zinc mixed solution, slowly add 52.535g (0.25mol) C
6H
8O
7H
2O, at 50 ℃, rotating speed 10r/min, constant temperature magnetic agitation 120min is again to wherein adding 11.88g (0.06mol) C
6H
12O
6H
2O, again at 50 ℃, rotating speed 10r/min, constant temperature magnetic agitation 120min obtains even slurry, and the mol ratio of carbon atom and zinc-iron atom is 9.92:4.
Four, even slurry is moved in the baking oven, be warming up to 110 ℃ with 0.5 ℃/min heating rate from room temperature, insulation 24h naturally cools to room temperature in the stove.
Five, material is put into planetary ball mill, ball milling 2h, ratio of grinding media to material is 20:1, obtains powder and moves in the Muffle furnace, argon flow amount is 0.9L/min, is warming up to 750 ℃ with 0.5 ℃/min heating rate from room temperature, natural cooling in the heat treatment 24h, stove.
Six, once more powder is put into planetary ball mill, ball milling 2h, ratio of grinding media to material is 20:1, and the powder 200 order mesh that sieve are obtained the composite cathode material for lithium ion cell that average grain diameter is 10 ~ 60 μ m.
As shown in Figure 1, the composite cathode material for lithium ion cell of embodiment 1 is for porous C clading ZnO and FeO particle form heterogeneous mixed uniformly compound system.Particle diameter is D
10=3.55 μ m, D
50=16.46 μ m, D
90=41.57 μ m, specific area is 6.2m
2/ g, wherein ZnO is that cross section is hexagonal Wurzite structure, FeO presents irregular contour structures.
As shown in Figure 2, the composite cathode material for lithium ion cell XRD figure spectrum of embodiment 1 represents the compound of ZnO and FeO, and no dephasign exists, because the carbon coated material is an amorphous phase, so corresponding diffraction maximum in collection of illustrative plates, do not occur.
As shown in Figure 3, the composite cathode material for lithium ion cell manufacturing and simulating battery of employing embodiment 1 is in the voltage range of 0.001 ~ 3V; Current density with 100mA/g is carried out charge-discharge test, and first discharge specific capacity reaches 1064mAh/g, and a very long platform is arranged near 0.75V; The initial charge specific capacity reaches 707mAh/g; Coulombic efficiency is 67% first, and coulombic efficiency subsequently is all more than 98%, and along with the circulation coulombic efficiency is tending towards 100% gradually.
As shown in Figure 4, through 80 times circulation, charging and discharging capacity is stabilized in more than the 400mAh/g, explains that this composite material has good cyclical stability.The electrochemical property test result sees table 1.
One, takes by weighing 67.9g (0.5mol) ZnCl
2Be dissolved in the 300ml deionized water, 50 ℃ of temperature, rotating speed 25r/min, magnetic agitation 30min obtains the zinc solution that zinc atom concentration is 1.67mol/L.Take by weighing 202g (0.5mol) Fe (NO again
3)
39H
2O is dissolved in another 300ml deionized water, 50 ℃ of temperature, and rotating speed 25r/min, magnetic agitation 30min obtains the iron salt solutions that iron atom concentration is 1.67mol/L.
Two, zinc solution is mixed with iron salt solutions, zinc salt and molysite mol ratio are 1:1,50 ℃ of temperature, and rotating speed 25r/min, magnetic agitation 30min obtains iron zinc mixed solution.
Three, in iron zinc mixed solution, slowly add 105g (0.5mol) C
6H
8O
7H
2O, at 70 ℃, rotating speed 25r/min, constant temperature magnetic agitation 30min is again to wherein adding 12g (0.06mol) C
6H
12O
6H
2O, again at 70 ℃, rotating speed 25r/min, constant temperature magnetic agitation 30min obtains even slurry, and the mol ratio of carbon atom and zinc-iron atom is 13.44:4.
Four, even slurry is moved in the baking oven, be warming up to 50 ℃ with 3 ℃/min heating rate from room temperature, insulation 48h naturally cools to room temperature in the stove.
Five, material is put into planetary ball mill, ball milling 10h, ratio of grinding media to material is 10:1, obtains powder, powder is moved in the rotary furnace again, nitrogen flow is 2L/min, is warming up to 900 ℃ with 0.5 ℃/min heating rate from room temperature, natural cooling in the heat treatment 14h, stove.
Six, ball milling 10h, ratio of grinding media to material is 10:1, obtains powder, the 200 order mesh that sieve obtain the composite cathode material for lithium ion cell that average grain diameter is 10 ~ 60 μ m.
This composite cathode material for lithium ion cell is made up of porous carbon materials clading ZnO and FeO particle.Its particle diameter is D
10=3.8 μ m, D
50=13.55 μ m, D
90=39.87 μ m, specific area is 6.9m
2/ g.After adopting the composite cathode material for lithium ion cell manufacturing and simulating battery of embodiment 2, carry out electrochemical property test, the result sees table 1.
Embodiment 3
One, takes by weighing 45.9g (0.25mol) Zn (CH
3COO)
22H
2O is dissolved in the 50ml deionized water, 40 ℃ of temperature, and rotating speed 15r/min, magnetic agitation 100min obtains the zinc solution that zinc atom concentration is 5mol/L.Take by weighing 324.42g (2mol) FeCl again
3Be dissolved in another 200ml deionized water, 40 ℃ of temperature, rotating speed 15r/min, magnetic agitation 100min obtains the iron salt solutions that iron atom concentration is 10mol/L.
Two, zinc solution is mixed with iron salt solutions, zinc salt and molysite mol ratio are 1:8,40 ℃ of temperature, and rotating speed 15r/min, magnetic agitation 100min obtains iron zinc mixed solution.
Three, in iron zinc mixed solution, slowly add 34.23g (0.1mol) C
12H
22O
11, at 100 ℃, rotating speed 15r/min, constant temperature magnetic agitation 30min obtains even slurry, and the mol ratio of carbon atom and zinc-iron atom is 2.12:4.
Four, even slurry is moved in the baking oven, be warming up to 200 ℃ with 1 ℃/min heating rate from room temperature, insulation 5h naturally cools to room temperature in the stove.
Five, material is put into planetary ball mill, ball milling 5h, ratio of grinding media to material is 15:1, obtains powder, powder is moved in the rotary furnace again, nitrogen flow is 1.5L/min, is warming up to 700 ℃ with 5 ℃/min heating rate from room temperature, natural cooling in the heat treatment 24h, stove.
Six, ball milling 5h, ratio of grinding media to material is 15:1, obtains powder, the 200 order mesh that sieve obtain the composite cathode material for lithium ion cell that average grain diameter is 10 ~ 60 μ m.
This composite material is made up of porous carbon materials clading ZnO and FeO particle.Its particle diameter is D
10=14.81 μ m, D
50=32.86 μ m, D
90=61.23 μ m, its specific area is 4.12m
2/ g.After adopting the composite cathode material for lithium ion cell manufacturing and simulating battery of embodiment 3, carry out electrochemical property test, the result sees table 1.
Embodiment 4
One, takes by weighing 45.9g (0.25mol) Zn (CH
3COO)
22H
2O is dissolved in the 50ml deionized water, 40 ℃ of temperature, and rotating speed 15r/min, magnetic agitation 100min obtains the zinc solution that zinc atom concentration is 5mol/L.Take by weighing 324.42g (2mol) FeCl again
3Be dissolved in another 200ml deionized water, 40 ℃ of temperature, rotating speed 15r/min, magnetic agitation 100min obtains the iron salt solutions that iron atom concentration is 10mol/L.
Two, zinc solution is mixed with iron salt solutions, zinc salt and molysite mol ratio are 1:8,40 ℃ of temperature, and rotating speed 15r/min, magnetic agitation 100min obtains iron zinc mixed solution.
Three, in iron zinc mixed solution, slowly add 17.11g (0.05mol) C
12H
22O
11, at 100 ℃, rotating speed 15r/min, constant temperature magnetic agitation 30min obtains even slurry, and the mol ratio of carbon atom and zinc-iron atom is 1.07:4.
Four, even slurry is moved in the baking oven, be warming up to 200 ℃ with 1 ℃/min heating rate from room temperature, insulation 5h naturally cools to room temperature in the stove.
Five, material is put into planetary ball mill, ball milling 5h, ratio of grinding media to material is 15:1, obtains powder, powder is moved in the rotary furnace again, nitrogen flow is 1.5L/min, is warming up to 700 ℃ with 5 ℃/min heating rate from room temperature, natural cooling in the heat treatment 24h, stove.
Six, ball milling 5h, ratio of grinding media to material is 15:1, obtains powder, the 200 order mesh that sieve obtain the composite cathode material for lithium ion cell that average grain diameter is 10 ~ 60 μ m.
This composite material is made up of porous carbon materials clading ZnO and FeO particle.Its particle diameter is D
10=13.7 μ m, D
50=30.26 μ m, D
90=50.5 μ m, its specific area is 4.85m
2/ g.After adopting the composite cathode material for lithium ion cell manufacturing and simulating battery of embodiment 4, carry out electrochemical property test, the result sees table 1.
One, takes by weighing 223.1g (0.75mol) Zn (NO
3)
26H
2O is dissolved in the 75ml deionized water, 30 ℃ of temperature, and rotating speed 15r/min, magnetic agitation 90min obtains the zinc solution that zinc atom concentration is 10mol/L.Take by weighing 61.2g (0.25mol) FeC again
6H
5O
7Be dissolved in another 2.5L deionized water, 30 ℃ of temperature, rotating speed 15r/min, magnetic agitation 90min obtains the iron salt solutions that iron atom concentration is 0.1mol/L.
Two, zinc solution is mixed with iron salt solutions, zinc salt and molysite mol ratio are 3:1,30 ℃ of temperature, and rotating speed 15r/min, magnetic agitation 90min obtains iron zinc mixed solution.
Three, in iron zinc mixed solution, slowly add 7.92g (0.04mol) C
6H
12O
6H
2O, at 90 ℃, rotating speed 15r/min, constant temperature magnetic agitation 180min obtains even slurry, and the mol ratio of carbon atom and zinc-iron atom is 0.96:4.
Four, even slurry is moved in the baking oven, be warming up to 100 ℃ with 3 ℃/min heating rate from room temperature, insulation 24h naturally cools to room temperature in the stove.
Five, material is put into planetary ball mill, ball milling 2h, ratio of grinding media to material is 20:1, obtains powder, powder is moved in the Muffle furnace again, nitrogen flow is 1L/min, is warming up to 700 ℃ with 4 ℃/min heating rate from room temperature, natural cooling in the heat treatment 24h, stove.
Six, ball milling 2h, ratio of grinding media to material is 20:1, obtains powder, the 200 order mesh that sieve obtain the composite cathode material for lithium ion cell that average grain diameter is 10 ~ 60 μ m.
This composite material directly is made up of ZnO and FeO particle, does not have carbon to coat phenomenon.Its particle diameter is D
10=20.15 μ m, D
50=43.16 μ m, D
90=70.23 μ m, its specific area is 3.55m
2/ g.After adopting the composite cathode material for lithium ion cell manufacturing and simulating battery of embodiment 5, carry out electrochemical property test, the result sees table 1.
One, takes by weighing 27.24g (0.2mol) ZnC
12Be dissolved in the 2L deionized water, 40 ℃ of temperature, rotating speed 15r/min, magnetic agitation 100min obtains the zinc solution that zinc atom concentration is 0.1mol/L.Take by weighing 162.21g (1mol) FeCl again
3Be dissolved in another 300ml deionized water, 40 ℃ of temperature, rotating speed 15r/min, magnetic agitation 100min obtains the iron salt solutions that iron atom concentration is 3.34mol/L.
Two, zinc solution is mixed with iron salt solutions, zinc salt and molysite mol ratio are 1:5,40 ℃ of temperature, and rotating speed 15r/min, magnetic agitation 100min obtains iron zinc mixed solution.
Three, in iron zinc mixed solution, slowly add 3.96g (0.02mol) C
6H
12O
6H
2O, at 100 ℃, rotating speed 10r/min, constant temperature magnetic agitation 90min is again to wherein adding 4.2g (0.02mol) C
6H
8O
7H
2O, again at 100 ℃, rotating speed 10r/min, constant temperature magnetic agitation 90min obtains even slurry, and the mol ratio of carbon atom and zinc-iron atom is 0.8:4.
Four, even slurry is moved in the baking oven, be warming up to 150 ℃ with 2 ℃/min heating rate from room temperature, insulation 12h naturally cools to room temperature in the stove.
Five, material is put into planetary ball mill, ball milling 2h, ratio of grinding media to material is 10:1, obtains powder, powder is moved in the rotary furnace again, nitrogen flow is 1L/min, is warming up to 700 ℃ with 3 ℃/min heating rate from room temperature, natural cooling in the heat treatment 24h, stove.
Six, ball milling 8h, ratio of grinding media to material is 10:1, obtains powder, the 200 order mesh that sieve obtain the composite cathode material for lithium ion cell that average grain diameter is 10 ~ 60 μ m.
This composite material directly is made up of ZnO and FeO particle, does not have carbon to coat phenomenon.Its particle diameter is D
10=18.24 μ m, D
50=30.27 μ m, D
90=62.45 μ m, its specific area is 4.67m
2/ g behind the composite cathode material for lithium ion cell manufacturing and simulating battery of employing embodiment 6, carries out electrochemical property test, and the result sees table 1.
Embodiment 7
One, takes by weighing 27.24g (0.2mol) ZnC
L2Be dissolved in the 2L deionized water, 40 ℃ of temperature, rotating speed 15r/min, magnetic agitation 100min, obtaining zinc atom concentration is the 0.1mol/L zinc solution.Take by weighing 162.21g (1mol) FeCl again
3Be dissolved in another 300ml deionized water, 40 ℃ of temperature, rotating speed 15r/min, magnetic agitation 100min, obtaining iron atom concentration is the 3.34mol/L iron salt solutions.
Two, zinc solution is mixed with iron salt solutions, zinc salt and molysite mol ratio are 1:5,40 ℃ of temperature, and rotating speed 15r/min, magnetic agitation 100min obtains iron zinc mixed solution.
Three, in iron zinc mixed solution, slowly add 0.396g (0.002mol) C
6H
12O
6H
2O, at 100 ℃, rotating speed 10r/min, constant temperature magnetic agitation 90min is again to wherein adding 0.42g (0.002mol) C
6H
8O
7H
2O, again at 100 ℃, rotating speed 10r/min, constant temperature magnetic agitation 90min obtains even slurry, and the mol ratio of carbon atom and zinc-iron atom is 0.08:4.
Four, even slurry is moved in the baking oven, be warming up to 150 ℃ with 2 ℃/min heating rate from room temperature, insulation 12h naturally cools to room temperature in the stove.
Five, material is put into planetary ball mill, ball milling 2h, ratio of grinding media to material is 10:1, obtains powder, powder is moved in the rotary furnace again, nitrogen flow is 1L/min, is warming up to 700 ℃ with 3 ℃/min heating rate from room temperature, natural cooling in the heat treatment 24h, stove.
Six, ball milling 8h, ratio of grinding media to material is 10:1, obtains powder, the 200 order mesh that sieve obtain the composite cathode material for lithium ion cell that average grain diameter is 10 ~ 60 μ m.
This composite material directly is made up of ZnO and FeO particle, does not have carbon to coat phenomenon.Its particle diameter is D
10=16.4 μ m, D
50=26.7 μ m, D
90=52.85 μ m, its specific area is 4.96m
2/ g behind the composite cathode material for lithium ion cell manufacturing and simulating battery of employing embodiment 7, carries out electrochemical property test, and the result sees table 1.
Comparative Examples 1 is made the active material of lithium ion battery negative material with commercially available ZnO powder after 200 order mesh sieve, use the method manufacturing and simulating battery identical with embodiment, carries out electrochemical property test by the method identical with embodiment, and the result sees table 1.
Comparative Examples 2; " carbon, the preparation of ZnO/ carbon porous microsphere and the application study on lithium ion battery negative thereof " (Cao Yang; Central China Normal University's master thesis; 2009) the nano-ZnO particle described in is as the lithium ion battery negative material active material, and its electrochemical property test result relatively sees table 1.
Comparative Examples 3; " Nano-sized transition-metal oxides asnegative-electrode materials for lithium-ion batteries " (lithium ion battery is made negative material with nano transition metal oxides, P.Poizot, S.Laruelle; S.Grugeon et al.Nature; 2000,407:496 ~ 499) the FeO particle described in is as the lithium ion battery negative material active material, and its electrochemical property test result relatively sees table 1.
Test result by table 1 finds out, embodiment 1,2,3 and 4 reversible capacity first are at 702.9 ~ 745mAh/g, and the 50 all reversible specific capacities that circulate remain on more than the 412.7mAh/g, and capability retention is more than 55.7%.The reversible capacity first that embodiment 5,6 and 7 obtains all more than 811.6mAh/g, wants high than embodiment 1,2,3 and 4, but circulates below the later capacity 403.8mAh/g of 50 weeks, and conservation rate is below 50%, and is low than embodiment 1,2,3 and 4.The reversible capacity first that Comparative Examples 1,2 and 3 obtains circulates 50 all reversible specific capacities below 371mAh/g all at 500 ~ 760mAh/g, and is all low than 50 all reversible specific capacities among the embodiment.This shows; Although two kinds of composite cathode material for lithium ion cell ZnO/FeO of the present invention and ZnO/FeO/C are micron particles; But compare single nano grade transition metal oxide and still show the specific capacity height; Have extended cycle life, stability is good, so composite material of the present invention more is applicable to the negative material that energy-storage battery and electrokinetic cell are used.
The electrochemical property test of table 1 embodiment and Comparative Examples
Claims (10)
1. composite cathode material for lithium ion cell; It is characterized in that: said composite cathode material for lithium ion cell is the ZnO/FeO composite material that ZnO and FeO form; ZnO is 1 ~ 24:8 with the ratio of the amount of substance of FeO, or the ZnO/FeO/C composite material of porous carbon C clading ZnO and FeO formation, and C is 1 ~ 14:4 with the ratio of the amount of substance of ZnO, FeO sum; The average grain diameter of ZnO/FeO composite material and ZnO/FeO/C composite material is 10 ~ 60 μ m, and specific area is 1 ~ 20m
2/ g.
2. the preparation method of a composite cathode material for lithium ion cell; May further comprise the steps: one, with zinc nitrate, zinc chloride or zinc acetate zinc solution and ferric nitrate, iron chloride or ironic citrate iron salt solutions; Press the ratio 1 ~ 24:8 of zinc salt and molysite amount of substance, mix obtaining iron zinc mixed solution; Two, the organic matter pyrolysis carbon matrix precursor is added in the iron zinc mixed solution, temperature is 50 ~ 100 ℃, and rotating speed is 10 ~ 25r/min, stirs 30 ~ 180min, obtains even slurry; Said organic matter pyrolysis carbon matrix precursor is more than one in citric acid, glucose, phenolic resins, epoxy resin and the sucrose; The organic matter pyrolysis carbon matrix precursor is pressed the ratio of carbon atom and the amount of zinc-iron atom species; Be (0＜carbon atom amount of substance≤1): (amounts of 4 zinc-iron atom species), or (amount of 1＜carbon atom amount of substance≤14:4 zinc-iron atom species); Three, even slurry is warming up to 50 ~ 200 ℃ with 0.5 ~ 3 ℃/min heating rate from room temperature, heat preservation solidification 5 ~ 48h naturally cools to room temperature in the stove; Four, at protective atmosphere nitrogen or argon gas; Flow is under 0.9 ~ 2L/min condition, is warming up to 700 ~ 900 ℃ with 0.5 ~ 5 ℃/min heating rate from room temperature, constant temperature sintering 14 ~ 24h; Naturally cool to room temperature in the stove; Obtaining composite cathode material for lithium ion cell, is the ZnO/FeO composite material of ZnO and FeO formation, or the ZnO/FeO/C composite material of porous carbon C clading ZnO and FeO formation.
3. the preparation method of composite cathode material for lithium ion cell according to claim 2 is characterized in that: said heat preservation solidification 5 ~ 48h, naturally cool to room temperature in the stove after; Put into planetary ball mill; Ball milling 2 ~ 10h, ball material mass ratio is 10 ~ 20:1, ball material is a stainless shot; Diameter is 10mm, obtains the powder that average grain diameter is 10 ~ 200 μ m.
4. the preparation method of composite cathode material for lithium ion cell according to claim 2 is characterized in that: said constant temperature sintering 14 ~ 24h, naturally cool to room temperature in the stove after; Put into planetary ball mill; Ball milling 2 ~ 10h, ball material mass ratio is 10 ~ 20:1, ball material is a stainless shot; Diameter is 10mm, and sieving through 200 orders obtains the composite cathode material for lithium ion cell that average grain diameter is 10 ~ 60 μ m.
5. the preparation method of composite cathode material for lithium ion cell according to claim 2, it is characterized in that: is that 0.1 ~ 10mol/L is dissolved in the deionized water with zinc nitrate, zinc chloride or zinc acetate by zinc atom concentration, obtains zinc solution; Is that 0.1 ~ 10mol/L is dissolved in the deionized water with ferric nitrate, iron chloride or ironic citrate by iron atom concentration, obtains iron salt solutions.
6. the preparation method of composite cathode material for lithium ion cell according to claim 5; It is characterized in that: said is that 0.1 ~ 10mol/L is dissolved in the deionized water with zinc nitrate, zinc chloride or zinc acetate by zinc atom concentration; Temperature is 25 ~ 50 ℃; Rotating speed is 10 ~ 25r/min, and the time is 30 ~ 180min; Said is that 0.1 ~ 10mol/L is dissolved in the deionized water with ferric nitrate, iron chloride or ironic citrate by iron atom concentration, and temperature is 25 ~ 50 ℃, and rotating speed is 10 ~ 25r/min, and the time is 30 ~ 180min.
7. the preparation method of composite cathode material for lithium ion cell according to claim 2; It is characterized in that: said zinc solution and iron salt solutions; In temperature is 10 ~ 50 ℃, and rotating speed is 10 ~ 25r/min, and the time is to mix under 30 ~ 180min condition to obtain iron zinc mixed solution.
8. the preparation method of composite cathode material for lithium ion cell according to claim 2, it is characterized in that: when said organic matter pyrolysis carbon matrix precursor was two or more, every kind of material added respectively, was under 10 ~ 25r/min at rotating speed respectively, stirred 30 ~ 180min.
9. the preparation method of composite cathode material for lithium ion cell according to claim 2 is characterized in that: said step 1, press the ratio 1.6 ~ 8:8 of zinc salt and molysite amount of substance; Said step 2, temperature are 70 ~ 100 ℃, and rotating speed is 10 ~ 15r/min; Stir 30 ~ 120min; The organic matter pyrolysis carbon matrix precursor is pressed the ratio of carbon atom and the amount of zinc-iron atom species, is 0.08＜carbon atom amount of substance≤0.96:4, or 2.12＜carbon atom amount of substance≤13.44:4; Said step 3 is warming up to 100 ~ 150 ℃ with 1 ~ 3 ℃/min heating rate from room temperature, heat preservation solidification 5 ~ 24h; Said step 4, flow are 0.9 ~ 1.5L/min, are warming up to 700 ~ 750 ℃ with 0.5 ~ 4 ℃/min heating rate from room temperature.
10. the preparation method of composite cathode material for lithium ion cell according to claim 9 is characterized in that: said step 1, press the ratio 4:8 of zinc salt and molysite amount of substance; Said step 2, temperature are 90 ℃, and rotating speed is 15r/min, stir 90min, and the organic matter pyrolysis carbon matrix precursor is pressed the ratio of carbon atom and the amount of zinc-iron atom species, is 0.8:4, or 9.92:4; Said step 3 is warming up to 110 ℃ with 2 ℃/min heating rate from room temperature, heat preservation solidification 12h; Said step 4, flow are 1L/min, are warming up to 700 ℃ with 3 ℃/min heating rate from room temperature, constant temperature sintering 24h.
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| CN109647584A (en) * | 2018-12-10 | 2019-04-19 | 桂林理工大学 | A kind of sand milling method of modifying of lithium ion battery mineral negative electrode material |
| CN110371924A (en) * | 2019-07-25 | 2019-10-25 | 许昌学院 | A kind of Fe2O3Porous nano line electrode material, preparation method and application |
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