CN103490046B - A kind of rich lithium manganese base solid solution/graphene composite material and preparation method thereof - Google Patents
A kind of rich lithium manganese base solid solution/graphene composite material and preparation method thereof Download PDFInfo
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- CN103490046B CN103490046B CN201310428730.7A CN201310428730A CN103490046B CN 103490046 B CN103490046 B CN 103490046B CN 201310428730 A CN201310428730 A CN 201310428730A CN 103490046 B CN103490046 B CN 103490046B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a kind of rich lithium manganese base solid solution/graphene composite material and preparation method thereof, be applicable to technical field of energy material.Described rich lithium manganese base solid solution general structure of the present invention is xLi
2mnO
3(1-x) LiMO
2, wherein M is any one in Ni, Co, Mn, Cr, Ni-Co, Ni-Mn, Ni-Co-Mn, Fe and Ru, 0 & lt; X & lt; 1; It is characterized in that described rich lithium manganese base solid solution is scattered in the interlayer of lamellar graphite alkene in granular form.Rich lithium manganese base solid solution/graphene composite material of the present invention can be used as anode material for lithium-ion batteries, effectively can improve the conductivity of rich lithium manganese base solid solution.Described preparation method has the advantages that technique is simple, with low cost, be suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of rich lithium manganese base solid solution/graphene composite material and preparation method thereof, belong to electrochemistry and field of material synthesis technology.
Background technology
Layer structure rich lithium manganese base solid solution positive electrode xLi
2mnO
3(1-x) LiMO
2the theoretical specific capacity of (wherein M is transition metal, 0<x<1) is more than 300mAhg
-1, reality can utilize capacity to be greater than 250mAhg
-1, be about 2 times of current positive electrode actual capacity used; In addition, a large amount of Mn element due to this materials'use, with LiCoO
2and LiNi
1/3mn
1/3co
1/3o
2compare, also have that cost is low, fail safe good, advantages of environment protection.Therefore, xLi
2mnO
3(1-x) LiMO
2be regarded as the ideal chose of anode material for lithium-ion batteries of future generation.But its poor high rate performance limits it and business-likely to further develop.
Solve rich lithium manganese base solid solution material Problems existing, first Water demand causes the profound cause of these problems.The rich poor high rate performance of lithium material of stratiform and the bad conductivity of this material itself and Li
+diffusion velocity is relevant slowly.
For the problems referred to above, scientific worker has done unremitting effort, mainly at present studies from following three aspects: 1. electrode material granules nanometer; 2. carry out bulk phase-doped; 3. with conductive materials as carbon or carbon nano-tube are carried out coated to material, to improve its apparent electronic conductivity.First two is all from microstructure to improve the high rate performance of material, but improving conductivity fundamentally could overcome the poor problem of high rate performance.Although be a kind of method improving material electronics conductivity with conductive materials this material coated, the effectiveness comparison improved is poor, because coated amount is too much unsuitable.Coatedly blocked uply Li can be increased
+the obstacle of diffusive migration, is unfavorable for the carrying out of electrode reaction dynamic process, causes material discharging capacity to reduce; Coated amount is less, then not obvious to the improvement effect of material electronics conductivity.Therefore, be necessary separately to ward off path to improve the electronic conductivity of material.
Graphene is the minimum material of known at present resistivity.The valence band of Graphene and conduction band partially overlap Fermi level place, to be energy gap be zero two-dimensional semiconductor, charge carrier can not by being scattered in sub-micron apart from interior motion.Graphene can be widely used in the preparation of composite material because of its good conductivity.Therefore, the problem that rich lithium manganese base solid solution/graphene composite material effectively can solve stratiform rich lithium material high rate performance difference is prepared.
Summary of the invention
The object of the invention is to overcome the defect of rich lithium manganese base solid solution as the high rate performance difference existing for anode material for lithium-ion batteries, prepare the anode material for lithium-ion batteries had compared with high-multiplying power discharge specific capacity, excellent high rate cyclic performance.The invention provides a kind of novel rich lithium manganese base solid solution/graphene composite material and preparation method thereof, the feature of described composite material is that rich lithium manganese base solid solution Granular composite is in the interlayer of lamellar graphite alkene, cause when discharge and recharge thus, Graphene can be rich lithium manganese base solid solution and provides more conductiving point and conductive path, thus improves the bulk electrical conductivity of this composite material.The rich lithium manganese base solid solution microscopic particles be wherein dispersed between graphene layer is about 4-8 μm, and lamellar graphite alkene thickness is about 1-25nm.
Rich lithium manganese base solid solution of the present invention has following general formula: xLi
2mnO
3(1-x) LiMO
2; Wherein M is transition metal, is preferably any one in Ni, Co, Mn, Cr, Ni-Co, Ni-Mn, Ni-Co-Mn, Fe and Ru, is more preferably Ni-Co, Ni-Mn, Ni-Co-Mn, most preferably is Ni-Co-Mn; 0<x<1, preferred 0.3-0.7, more preferably 0.4-0.6.
The preparation of rich lithium manganese base solid solution/graphene composite material of the present invention is prepared by following method, and described method comprises the steps:
(1) presoma of rich lithium manganese base solid solution/graphene oxide doped material is prepared by coprecipitation or solvent-thermal method;
(2) by described presoma precalcining;
(3) make the described presoma generation solid phase reaction through precalcining, thus obtain rich lithium manganese base solid solution/graphene oxide doped material;
(4) gained dopant material is mixed with graphene oxide, reduce subsequently, thus obtain described rich lithium manganese base solid solution/graphene composite material.
Hereafter will specifically describe each step:
the presoma of rich lithium manganese base solid solution/graphene oxide doped material is prepared by coprecipitation
Described coprecipitation comprises the mixed solution of the salt using comprising M and Mn, the NaOH solution as precipitation reagent and the ammonia spirit as complexing agent and is added in liquid at the bottom of Graphene simultaneously, thus make the salt co-precipitation of M and Mn, then products therefrom is mixed with lithium compound.Particularly, described coprecipitation comprises:
(1) according to the required metering ratio preparation salt of M and the mixed solution of Mn salt;
(2) under inert gas shielding, described mixture solution, the NaOH solution as precipitation reagent and the ammonia spirit as complexing agent are added in the reactor containing liquid at the bottom of graphene oxide simultaneously and react;
(3) product of step (2) is mixed with lithium compound, and properly carry out ball milling.
Transition metal ions ratio in described coprecipitation step (1) is by the ratio-dependent of M and Mn in required rich lithium manganese base solid solution structural formula.Wherein, transition metal ions total concentration is unimportant, is generally 0.6-1.0molL
-1, be more preferably 0.6-0.9molL
-1, most preferably be 0.6-0.8molL
-1.The salt of M and Mn in step (1) can be organic salt or the inorganic salts of respective metal, and condition is that it is at room temperature in water soluble.Such as, described salt can be one or more in acetate, nitrate or sulfate.Lithium compound in step (3) can be one or more in acetate, nitrate or lithium hydroxide.
In described coprecipitation step (2) NaOH used and ammonia spirit consumption with metal ions M and Mn consumption and change, condition is enough to make described precipitation by metallic ion and complexing.Such as, the NaOH consumption in reactant mixture can be 1.0-4.0molL
-1, be preferably 1.0-3.0molL
-1, be more preferably 1.0-2.5molL
-1, based on overall reaction solution.The consumption of ammonia spirit is (with NH
3meter) can be 0.2-0.8molL
-1, be preferably 0.2-0.6molL
-1, be more preferably 0.2-0.5molL
-1, based on overall reaction solution.
Reaction temperature in step (2) is 30-80 DEG C, is preferably 40-70 DEG C, is more preferably 50-60 DEG C; Reaction time is 2-36h, is preferably 6-28h, is more preferably 10-26h, most preferably is 12-24h.
The amount of graphene oxide used in described coprecipitation step (2) can change as required, such as raw material total amount (total weight of M salt and Mn salt) and graphene oxide weight ratio are 10:0.1-10:0.8, be preferably 10:0.2-10:0.7, be preferably 10:0.4-10:0.6.
After coprecipitation reaction terminates, by products therefrom suction filtration, washing, vacuumize to obtain described presoma.
Co-precipitation reactor used is CSTR reactor.
Lithium salts consumption used in step (3) is determined by required final rich lithium manganese base solid solution structural formula.Ball milling in step (3) can carry out under the existence of dispersant.Suitable dispersant is known in those skilled in the art, such as ethanol, acetone, benzinum etc.Ball-milling Time is unimportant, is generally 2-12 hour, is preferably 3-8 hour, is more preferably 4-6 hour.
the presoma of rich lithium manganese base solid solution/graphene oxide doped material is prepared by solvent-thermal method
Described solvent-thermal method comprises oxalic acid to be added into and comprises in the salt of Li, Mn and M and the dispersion of graphene oxide, thus solvent thermal reaction occurs, thus obtains the presoma of described rich lithium manganese base solid solution/graphene oxide doped material.Particularly, described solvent-thermal method comprises:
(1) according to required dopant material metering ratio, the salt of Li, Mn and M and graphene oxide are dissolved (salt for Li, Mn and M) or is scattered in (for graphene oxide) solvent, forms hybrid dispersions;
(2) prepare oxalic acid solution, added in the hybrid dispersions of gained in step (1);
(3) described solution is all proceeded in reactor, react, thus obtain the presoma of described rich lithium manganese base solid solution/graphene oxide doped material.
Transition metal ions ratio in described solvent-thermal method step (1) is by the ratio-dependent of M and Mn in required rich lithium manganese base solid solution structural formula.Wherein, transition metal ions total concentration is unimportant, is generally 0.6-1.0molL
-1, be more preferably 0.6-0.9molL
-1, most preferably be 0.6-0.8molL
-1.The salt of described Li, Mn and M can be organic salt or the inorganic salts of respective metal.Such as, described salt can be one or more in acetate, nitrate or sulfate.Raw material total amount (total weight of the salt of Li, Mn and M) is 10:0.1-10:1 with the weight ratio of graphene oxide, is preferably 10:0.1-10:0.8, is more preferably 10:0.2-10:0.7, most preferably is 10:0.4-10:0.6.
Solvent in step (1) is Yi Chun ﹑ methyl alcohol, is preferably ethanol.
In described solvent-thermal method step (2), concentration and the consumption of oxalic acid solution have no particular limits, and condition is that it with described transition metal ions, sufficient solvent thermal reaction can occur.Such as, the concentration of oxalic acid solution can be 0.3-2.0molL
-1, be preferably 0.5-1.5molL
-1, be more preferably 0.8-1.2molL
-1.The consumption (with oxalic acid: M molar ratio computing) of oxalic acid can be 2.0:1-1.0:1, is preferably 1.6:1-1.0:1, is more preferably 1.5:1-1.0:1.
Reaction temperature in described solvent-thermal method step (3) is generally 100-300 DEG C, is preferably 150-250 DEG C, is more preferably 180-220 DEG C.Reaction time is generally 2-24 hour, is preferably 4-20 hour, is more preferably 10-18 hour.
precalcining
Precalcining is carried out to the presoma of obtained rich lithium manganese base solid solution/graphene oxide doped material.Precalcining temperature is generally 300-700 DEG C, is preferably 300-600 DEG C, is more preferably 300-500 DEG C.The precalcining time is generally 1-8 hour, is preferably 2-6 hour, is more preferably 3-5 hour.Described precalcining is carried out usually under an inert atmosphere.Inert gas used is such as nitrogen, argon gas etc.
solid phase reaction
The material of precalcining is sintered, thus solid phase reaction occurs.Solid phase reaction is carried out under an inert atmosphere.The time sintered under an inert atmosphere is 2-24 hour, is preferably 4-20 hour, is more preferably 8-18 hour.The temperature of solid phase reaction is 800-1000 DEG C, is preferably 850-1000 DEG C, is more preferably 900-950 DEG C.After sintering, products therefrom is naturally cooled to room temperature, obtain described rich lithium manganese base solid solution/graphene oxide doped material thus.
dopant material mixes with graphene oxide and reduces
Gained dopant material is mixed with graphene oxide, reduces in reducing atmosphere subsequently, be cooled to room temperature, thus obtain described rich lithium manganese base solid solution/graphene composite material.The mixed proportion of described dopant material and graphene oxide has no particular limits, and can be arbitrary proportion as required, such as, is generally 10:0.1-10:1.0, is preferably 10:0.3-10:0.8, is more preferably 10:0.4-10:0.6, with mass ratio range.
Hybrid mode can be various usual manners known in the art, such as, be dry mixed, or the two is scattered in dispersant as in ethanol, then dry, wherein baking temperature can be such as 80 DEG C.
Described reduction can be carried out in tube furnace; Recovery time can be such as 1-24 hour, is preferably 4-20 hour, is more preferably 6-18 hour, most preferably is 8-16 hour.Reduction temperature can be 600-1100 DEG C, is preferably 700-1000 DEG C, is more preferably 800-950 DEG C, most preferably is 800-900 DEG C.Reducing atmosphere can be the mixture (its volume ratio is as being 1:0.1-1:100) of hydrogen or hydrogen and inert gas (as nitrogen, helium, neon etc.).
Advanced composite material (ACM) of the present invention can be used as the positive electrode of lithium ion battery.
Compared with pure rich lithium manganese base solid solution, advanced composite material (ACM) of the present invention and preparation method thereof tool has the following advantages:
(1) preparation process technique is simple, and the cycle is short, and efficiency is high, is produced on a large scale;
(2) design feature of the rich lithium manganese base solid solution/graphene composite material prepared is, after adopting graphene oxide once to adulterate to rich lithium manganese base solid solution, adopts again graphene oxide to carry out secondary finishing to it, finally reduces.Rich lithium manganese base solid solution Granular composite is between lamellar graphite alkene, and cause when discharge and recharge thus, Graphene can be rich lithium manganese base solid solution and provides more conductiving point and conductive path, thus improves the bulk electrical conductivity of this composite material;
(3) in rich lithium manganese base solid solution/graphene composite material of the present invention, the rich lithium manganese base solid solution microscopic particles be dispersed between graphene layer is about 4-8 μm, and lamellar graphite alkene thickness is about 1-25nm.
(4) high rate performance that is significantly improved of rich lithium manganese base solid solution of the present invention/graphene composite material tool, pure rich lithium manganese base solid solution is at 0.5C (100mAhg
-1) discharge and recharge time, discharge capacity is 200mAhg
-1, and composite material of the present invention is under identical multiplying power, discharge capacity can reach 258mAhg
-1, improve 58mAhg
-1.
Therefore, rich lithium manganese base solid solution/graphene composite material of the present invention successfully overcomes the defect of pure rich lithium manganese base solid solution, is a kind of anode material for lithium-ion batteries having application prospect.
Particularly, the present invention relates to following theme:
1. rich lithium manganese base solid solution/graphene composite material, wherein said rich lithium manganese base solid solution general structure is xLi
2mnO
3(1-x) LiMO
2, wherein M is any one in Ni, Co, Mn, Cr, Ni-Co, Ni-Mn, Ni-Co-Mn, Fe and Ru, 0<x<1; It is characterized in that described rich lithium manganese base solid solution is scattered in the interlayer of lamellar graphite alkene in granular form.
2., according to the rich lithium manganese base solid solution/graphene composite material of the 1st, it is characterized in that the rich lithium manganese base solid solution be dispersed between graphene layer is of a size of about 4-8 μm, lamellar graphite alkene thickness is about 1-25nm.
3. prepare the method according to the 1st or the rich lithium manganese base solid solution/graphene composite material of 2, it is characterized in that, described method comprises the steps:
(1) presoma of rich lithium manganese base solid solution/graphene oxide doped material is prepared by coprecipitation or solvent-thermal method;
(2) by described presoma precalcining;
(3) make the presoma generation solid phase reaction of described precalcining, thus obtain rich lithium manganese base solid solution/graphene oxide doped material;
(4) gained dopant material is mixed with graphene oxide, reduce subsequently, thus obtain described rich lithium manganese base solid solution/graphene composite material.
4. according to the method for the 3rd, it is characterized in that described coprecipitation comprises: be added in liquid at the bottom of Graphene using comprising the mixed solution of the salt of M and Mn, the NaOH solution as precipitation reagent and the ammonia spirit as complexing agent, thus make the salt co-precipitation of M and Mn, then products therefrom is mixed with lithium compound, thus prepare the presoma of described rich lithium manganese base solid solution/graphene oxide doped material.
5. according to the 3rd or the method for 4, it is characterized in that described solvent-thermal method comprises oxalic acid to be added into comprises in the salt of Li, Mn and M and the dispersion of graphene oxide, there is solvent thermal reaction thus, thus obtain the presoma of described rich lithium manganese base solid solution/graphene oxide doped material.
6. the method any one of 3-5, is characterized in that described precalcining is under an inert atmosphere in 300-700 DEG C, preferred 300-600 DEG C, more preferably carries out at the temperature of 300-500 DEG C.
7. the method any one of 3-6, is characterized in that described solid phase reaction is under an inert atmosphere in 800-1000 DEG C, is preferably 850-1000 DEG C, carries out under being more preferably the temperature of 900-950 DEG C.
8. the method any one of 3-7, is characterized in that described reduction is under reducing atmosphere, at 600-1100 DEG C, is preferably 700-1100 DEG C, is more preferably 800-950 DEG C, carries out under most preferably being the temperature of 800-900 DEG C.
9., according to the method for the 8th, reducing gas wherein used is the mixture of hydrogen or hydrogen and nitrogen.
10. according to the 1st or the rich lithium manganese base solid solution/graphene composite material of 2 as the purposes of the positive electrode of lithium ion battery.
Brief description
Fig. 1 is the TEM figure of the graphene oxide according to embodiment 1 preparation.
Fig. 2 is the XRD figure of the rich lithium manganese base solid solution/graphene composite material according to embodiment 1 preparation.
Fig. 3 is the high rate performance figure of the rich lithium manganese base solid solution/graphene composite material according to embodiment 1 preparation.
Fig. 4 is the SEM figure of the rich lithium manganese base solid solution prepared by solvent-thermal method according to embodiment 4.
Fig. 5 is the head week charge and discharge electrograph of rich lithium manganese base solid solution/graphene composite material under 0.5C prepared by solvent-thermal method according to embodiment 4.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1, using nitrate as raw material, adopts coprecipitation to prepare rich lithium manganese base solid solution/graphene composite material
(1) Ni (NO is prepared by required mole ratio (0.58:0.11:0.11)
3)
26H
2o, Co (NO
3)
26H
2o and Mn (NO
3)
2mixed solution, transition metal ions total concentration is 0.8molL
-1.Adopt 1.5molL
-1naOH solution as precipitation reagent, 0.3molL
-1ammonia spirit, as complexing agent, adds a certain amount of graphene oxide at CSTR reaction container bottom, its Raw total amount (Ni (NO
3)
26H
2o, Co (NO
3)
26H
2o and Mn (NO
3)
2) with graphene oxide weight ratio be 10:0.5;
(2) under inert gas shielding, three kinds of solution adopt and flow mode, add in the reactor containing liquid at the bottom of Graphene by peristaltic pump, control pH=11, mixing speed 1000rpm, reaction temperature 60 DEG C in course of reaction, reaction time 12h.After suction filtration, washing, vacuum, drying obtains Mn
0.58ni
0.11co
0.11(OH)
0.8/ graphene oxide presoma;
(3) mixed with certain mol proportion (1:1.06) ball milling with lithium acetate by the presoma obtained, period adds the ethanol of 10mL as dispersant.After ball milling, material dried, grind refinement, in 30MPa lower sheeting, first at 450 DEG C, carry out precalcining 8h in a nitrogen atmosphere, subsequently at 800 DEG C, in nitrogen atmosphere, high temperature sintering 12h, naturally cools to room temperature, obtains rich lithium manganese base solid solution/graphene oxide doped material;
(4) by the dopant material that obtains and graphene oxide (10:0.5 in certain proportion, weight ratio) again mix, be dispersed in 100mL ethanol, at 80 DEG C, constant temperature stirs dry, subsequently in tube furnace, in 900 DEG C, reduce 10h in a nitrogen atmosphere, naturally cool to room temperature, obtain rich lithium manganese base solid solution/graphene composite material.
SEM according to the rich lithium manganese base solid solution/graphene composite material of embodiment 1 preparation is illustrated in Fig. 1.
XRD according to the rich lithium manganese base solid solution/graphene composite material of embodiment 1 preparation is illustrated in Fig. 2.
High rate performance according to the rich lithium manganese base solid solution/graphene composite material of embodiment 1 preparation is illustrated in Fig. 3.From this figure, under 0.5C (100mA/g) discharging current, the discharge capacity of described composite material is 225mAhg
-1.
Embodiment 2, using sulfate as raw material, adopts coprecipitation to prepare rich lithium manganese base solid solution/graphene composite material
(1) NiSO is prepared by required mol ratio (0.58:0.11:0.11)
46H
2o ﹑ CoSO
47H
2o and MnSO
4h
2the mixed solution of O, transition metal ions total concentration is 1.0molL
-1.Adopt 2.0molL
-1naOH solution as precipitation reagent, 0.5molL
-1ammonia spirit, as complexing agent, adds a certain amount of graphene oxide at CSTR reaction container bottom, wherein raw material (NiSO
46H
2o ﹑ CoSO
47H
2o and MnSO
4h
2o) with graphene oxide weight ratio be 10:0.5;
(2) under inert gas shielding, three kinds of solution adopt and flow mode, add in the reactor containing liquid at the bottom of Graphene by peristaltic pump, control pH=11, mixing speed 1000rpm, reaction temperature 50 DEG C in course of reaction, reaction time 24h.Mn is obtained after suction filtration, washing, vacuumize
0.58ni
0.11co
0.11(OH)
0.8/ graphene oxide presoma;
(3) presoma obtained is mixed with certain mol proportion (1:1.06) ball milling with lithium hydroxide, add the ethanol of 100mL as dispersant.After ball milling, material dried, grind refinement, in 30MPa lower sheeting, first at 450 DEG C, carry out precalcining 3h in a nitrogen atmosphere, subsequently at 900 DEG C, high temperature sintering 16h, naturally cools to room temperature in an inert atmosphere, obtains rich lithium manganese base solid solution/graphene oxide doped material;
(4) by the dopant material that obtains and graphene oxide (10:0.5 in certain proportion, weight ratio) again mix, dispersion in ethanol, at 80 DEG C, constant temperature stirs dry, subsequently in tube furnace, in 700 DEG C, reduce 12h in a nitrogen atmosphere, naturally cool to room temperature, obtain rich lithium manganese base solid solution/graphene composite material.
Under 0.5C (100mA/g) discharging current, the discharge capacity of described composite material is 248mAhg
-1.
Embodiment 3 is using acetate as raw material, and methyl alcohol, as organic solvent, adopts solvent-thermal method to prepare rich lithium manganese base solid solution/graphene composite material.
(1) by the CH of mol ratio (0.58:0.11:0.11)
3cOOLi, (CH
3cOO)
2co, (CH
3cOO)
2mn, (CH
3cOO)
2ni and graphene oxide (raw material total amount (CH
3cOOLi, (CH
3cOO)
2co, (CH
3cOO)
2mn and (CH
3cOO)
2ni) be 10:0.5 with the weight ratio of graphene oxide) dissolve or disperse (for graphene oxide) in methyl alcohol, fully stir, formation hybrid dispersions;
(2) 1.0molL is prepared
-1oxalic acid solution, slowly join in the mixed solution that back formed by certain mol proportion (mol ratio of Co and Ni total ion concentration and oxalic acid is 1.3:1);
(3) at room temperature, magnetic agitation 2h, makes its pre-reaction;
(4) solution is all proceeded to reactor and react 10h at 200 DEG C;
At (5) 90 DEG C, water bath with thermostatic control is stirred dry, obtains presoma/graphene oxide composite material;
(6) presoma/graphene oxide composite material is put into tube furnace, at 550 DEG C, carry out precalcining 7h in a nitrogen atmosphere, obtain the presoma of high―temperature nuclei reaction; Then, at 900 DEG C, high temperature sintering 12h in a nitrogen atmosphere, namely obtains rich lithium manganese base solid solution/graphene oxide doped material;
(7) by the dopant material that obtains and graphene oxide (10:0.5 in certain proportion, weight ratio) again mix, dispersion in ethanol, at 80 DEG C, constant temperature stirs dry, subsequently in tube furnace, in 900 DEG C, in nitrogen, reduce 12h, naturally cool to room temperature, obtain rich lithium manganese base solid solution/graphene composite material.
Under 0.5C (100mA/g) discharging current, the discharge capacity of composite material is 250mAhg
-1.
Embodiment 4 is using acetate as raw material, and ethanol, as organic solvent, adopts solvent-thermal method to prepare rich lithium manganese base solid solution/graphene composite material.
(1) by the CH of chemical mol ratio (0.58:0.11:0.11)
3cOOLi, (CH
3cOO)
2co, (CH
3cOO)
2mn, (CH
3cOO)
2ni and graphene oxide are dissolved in ethanol, fully stir, and form mixed solution;
(2) 1.0molL is prepared
-1oxalic acid solution, slowly add in the mixed solution that back formed by certain mol proportion (the mol ratio 1.3:1 of Mn, Co and Ni total ion concentration and oxalic acid);
(3) at room temperature, magnetic agitation 2h, makes its pre-reaction;
(4) solution is all proceeded to reactor and react 18h at 180 DEG C;
At (5) 80 DEG C, water bath with thermostatic control is stirred dry, obtains presoma/graphene oxide composite material;
(6) presoma/graphene oxide composite material is put into tube furnace, at 400 DEG C, carry out precalcining 6h in a nitrogen atmosphere, obtain the presoma of high―temperature nuclei reaction; Then at 850 DEG C, in a nitrogen atmosphere, high temperature sintering 18h, namely obtains rich lithium manganese base solid solution/graphene oxide doped material (Fig. 4);
(7) by the dopant material that obtains and graphene oxide (10:0.5 in certain proportion, weight ratio) again mix, dispersion in ethanol, at 80 DEG C, constant temperature stirs dry, subsequently in tube furnace, in 950 DEG C, in nitrogen, reduce 12h, naturally cool to room temperature, obtain rich lithium manganese base solid solution/graphene composite material.
Under 0.5C (100mA/g) discharging current, the discharge capacity of composite material is 258mAhg
-1(Fig. 5).
Should be understood that, the above-mentioned statement for present pre-ferred embodiments is comparatively detailed, and therefore can not think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (17)
1. rich lithium manganese base solid solution/graphene composite material, wherein said rich lithium manganese base solid solution general structure is xLi
2mnO
3(1-x) LiMO
2, wherein M is any one in Ni, Co, Mn, Cr, Ni-Co, Ni-Mn, Ni-Co-Mn, Fe and Ru, 0<x<1; It is characterized in that, described rich lithium manganese base solid solution is scattered in the interlayer of lamellar graphite alkene in granular form.
2. rich lithium manganese base solid solution/graphene composite material according to claim 1, is characterized in that, the rich lithium manganese base solid solution be dispersed between graphene layer is of a size of 4-8 μm, and lamellar graphite alkene thickness is 1-25nm.
3. prepare a method for the rich lithium manganese base solid solution/graphene composite material according to claim 1 or 2, it is characterized in that, described method comprises the steps:
(1) presoma of rich lithium manganese base solid solution/graphene oxide doped material is prepared by coprecipitation or solvent-thermal method;
(2) by described presoma precalcining;
(3) make the presoma generation solid phase reaction of described precalcining, thus obtain rich lithium manganese base solid solution/graphene oxide doped material;
(4) gained dopant material is mixed with graphene oxide, reduce subsequently, thus obtain described rich lithium manganese base solid solution/graphene composite material.
4. method according to claim 3, it is characterized in that, described coprecipitation comprises: be added in liquid at the bottom of Graphene using comprising the mixed solution of the salt of M and Mn, the NaOH solution as precipitation reagent and the ammonia spirit as complexing agent, thus make the salt co-precipitation of M and Mn, then products therefrom is mixed with lithium compound, thus prepare the presoma of described rich lithium manganese base solid solution/graphene oxide doped material.
5. according to the method for claim 3 or 4, it is characterized in that, described solvent-thermal method comprises oxalic acid to be added into and comprises in the salt of Li, Mn and M and the dispersion of graphene oxide, there is solvent thermal reaction thus, thus obtain the presoma of described rich lithium manganese base solid solution/graphene oxide doped material.
6. the method any one of claim 3-4, is characterized in that, described precalcining is carried out under an inert atmosphere at the temperature of 300-700 DEG C.
7. method according to claim 6, is characterized in that, described precalcining is carried out under an inert atmosphere at the temperature of 300-600 DEG C.
8. method according to claim 7, is characterized in that, described precalcining is carried out under an inert atmosphere at the temperature of 300-500 DEG C.
9. the method any one of claim 3-4, is characterized in that, described solid phase reaction is carried out under an inert atmosphere at the temperature of 800-1000 DEG C.
10. method according to claim 9, is characterized in that, described solid phase reaction is carried out under an inert atmosphere at the temperature of 850-1000 DEG C.
11. methods according to claim 10, is characterized in that, described solid phase reaction is carried out under an inert atmosphere at the temperature of 900-950 DEG C.
12. methods any one of claim 3-4, it is characterized in that, described reduction, under reducing atmosphere, is carried out at the temperature of 600-1100 DEG C.
13. methods according to claim 12, is characterized in that, described reduction, under reducing atmosphere, is carried out at the temperature of 700-1100 DEG C.
14. methods according to claim 13, is characterized in that, described reduction, under reducing atmosphere, is carried out at the temperature of 800-950 DEG C.
15. methods according to claim 14, is characterized in that, described reduction, under reducing atmosphere, is carried out at the temperature of 800-900 DEG C.
16. methods according to claim 12, reducing gas wherein used is the mixture of hydrogen or hydrogen and nitrogen.
17. according to the rich lithium manganese base solid solution/graphene composite material of claim 1 or 2 purposes as the positive electrode of lithium ion battery.
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| JP6631012B2 (en) * | 2014-03-27 | 2020-01-15 | 東レ株式会社 | Method for producing lithium-rich cathode active material composite particles |
| CN104852053B (en) * | 2015-04-03 | 2017-10-31 | 郭建 | A kind of rate ternary cathode material of lithium ion battery presoma and preparation method thereof |
| CN105406047B (en) * | 2015-12-29 | 2018-07-13 | 北京工业大学 | A kind of synthetic method of conductive grid |
| CN105702926B (en) * | 2016-02-01 | 2018-07-06 | 浙江天能能源科技股份有限公司 | A kind of three-dimensional net structure ternary composite cathode material and preparation method thereof |
| CN106711435B (en) * | 2016-08-17 | 2023-04-07 | 重庆锦添翼新能源科技有限公司 | Preparation method of layered lithium-rich manganese-based/graphene nanoribbon positive electrode composite material |
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| CN108091863A (en) * | 2017-12-18 | 2018-05-29 | 江苏双登富朗特新能源有限公司 | Graphene is modified lithium-rich manganese-based anode material and preparation method thereof |
| CN109755549B (en) * | 2019-03-11 | 2020-04-28 | 清远佳致新材料研究院有限公司 | Nickel-based positive electrode material, preparation method thereof, lithium ion battery positive electrode, lithium ion battery and application |
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| CN103050683A (en) * | 2012-12-28 | 2013-04-17 | 深圳市贝特瑞新能源材料股份有限公司 | Polyphase manganese base solid solution composite cathode material and preparation method thereof |
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