CN107331853A - A kind of graphene composite multi-layer spherical manganic acid lithium electrode material with holes and its lithium ion battery of preparation - Google Patents

A kind of graphene composite multi-layer spherical manganic acid lithium electrode material with holes and its lithium ion battery of preparation Download PDF

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CN107331853A
CN107331853A CN201710709984.4A CN201710709984A CN107331853A CN 107331853 A CN107331853 A CN 107331853A CN 201710709984 A CN201710709984 A CN 201710709984A CN 107331853 A CN107331853 A CN 107331853A
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lithium
holes
electrode material
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graphene composite
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CN107331853B (en
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冯祥明
陈卫华
李子贺
宋轲铭
米立伟
郑金云
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Zhengzhou University
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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
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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Abstract

The present invention disclose it is a kind of can charge and discharge lithium ion graphene composite multi-layer spherical manganic acid lithium electrode material with holes and high voltage comprising the material can charge and discharge lithium ion battery.The multilayer spherical LiMn2O4 with holes is to be prepared from by presoma of manganese sesquioxide managnic oxide using solid phase method, the pattern with porous, layering and opening, is dispersed in the material after being combined around prepared lithium manganate particle to graphene sheet layer even structure.The high voltage can charge and discharge lithium ion battery be using graphene composite multi-layer spherical LiMn2O4 with holes as positive pole, lithium metal or or can embedding de- lithium active material be negative pole, soluble lithium salt organic solution be electrolyte.Graphene composite multi-layer spherical LiMn2O4 with holes disclosed by the invention has the advantages that high low cost, abundant raw material, voltage, good rate capability and cyclical stability are strong as lithium ion battery electrode material.Comprising the material can charge and discharge lithium ion battery there is high-energy-density and high power density, with wide market application foreground.

Description

A kind of graphene composite multi-layer spherical manganic acid lithium electrode material with holes and its preparation Lithium ion battery
Technical field
The invention belongs to field of lithium ion battery anode, and in particular to can charge and discharge lithium ion graphene composite multi-layer Spherical manganic acid lithium electrode material with holes and high-tension comprising the material can charge and discharge lithium ion batteries.
Background technology
The medium that lithium ion battery is transmitted as energy between new energy and electronic equipment, with its high specific energy, long circulating longevity The advantages of life, the equipment such as mobile phone, computer, electric automobile have been widely used in it.But towards communications and transportation of future generation, power network With the field such as the consumption electronic product of requirements at the higher level, current lithium ion battery can not meet requirement, therefore exploitation has height The lithium ion battery of voltage, high power density and high-energy-density turns into current active demand.
In lithium-ion battery system, influence of the positive electrode to battery performance is the most obvious.Compared to cobalt acid lithium, lithium manganese phosphate And ternary material, spinel lithium manganate has abundant manganese source, stable simple, the voltage height of synthesis technique, cost is low and security is good The advantages of, it has been successfully applied in lithium ion battery production, but poor high rate performance and the short cycle life big day of one's doom It has been made further to apply.Spinel lithium manganate causes the cyclical stability of material due to the dissolving of the Mn in electrochemical reaction Difference；And in big multiplying power, the lithium ion transport speed and electron conductivity of material are relatively low, material is set to be polarized under larger multiplying power sternly Weight, specific discharge capacity is relatively low.
Now, mainly by controlling pattern, bulk phase-doped and Material cladding solve problem above.Pattern control aspect, material Expect nanosizing and construct porous packed structures, lift ion transportation.In addition, by with the high conductivity material such as carbon is compound carries High electron conduction.But the too high dissolving for easily accelerating material of nano material activity, reduces stability, the mangaic acid of element doping Its cycle performance of lithium and multiplying power fail to be improved significantly.
The content of the invention
The spherical LiMn2O4 with holes of graphene composite multi-layer disclosed in this patent has novel unique pattern and uniform Graphene coated：The pattern of porous layering opening adds the space of electrolyte storage, shortens Li+The path of transmission, reduction Concentration polarization, successfully improves the ion diffusivity and cycle performance of material；Multilayer spherical LiMn2O4 with holes is by multiaspect Body crystal structure is constituted, and is effectively reduced Mn dissolving, is strengthened the cyclical stability of material；The dispersed bag of graphene Cover, making the electron conduction of material strengthens.Thus, material has high low cost, abundant raw material, voltage, good rate capability and followed The strong advantage of ring stability, comprising the material can charge and discharge lithium ion battery there is high-energy-density and high power density, have Wide market application foreground.
Realize the technical scheme is that：A kind of graphene composite multi-layer spherical manganic acid lithium electrode material with holes, stone Black alkene composite multi-layer spherical manganic acid lithium electrode material with holes is dispersed in lithium manganate particle week by the graphene uniform of lamellar structure Composition is enclosed, the LiMn2O4 is the multilayer spherical structure with holes that primary particle is accumulated, and the particle diameter of primary particle is 100- 200 nm, the particle diameter of the multilayer spherical manganic acid lithium electrode material with holes of accumulation is 1-5 μm.
The amount of graphene is the 1%- of LiMn2O4 quality in graphene composite multi-layer spherical manganic acid lithium electrode material with holes 20%。
The preparation method of the graphene composite multi-layer spherical manganic acid lithium electrode material with holes is as follows：
（1）Cetyl trimethylammonium bromide and ammonium bicarbonate solubility are formed into mixed solution one in deionized water；
（2）Manganese sulfate is dissolved in formation mixed solution two in deionized water；
（3）By step（1）Obtained mixed solution one is placed in 40-60 DEG C of oil bath, by step（2）Obtained mixed solution Two are added drop-wise in mixed solution one, and pH is adjusted after completion of dropping between 7-8, to obtain turbid solution；
（4）By step（3）Obtained turbid solution washing centrifugation, drying obtains the primary powder of manganese carbonate, manganese carbonate primary powder Calcined at 600-800 DEG C, obtain presoma manganese sesquioxide managnic oxide；
（5）By step（4）Obtained presoma manganese sesquioxide managnic oxide and lithium salts is added in absolute ethyl alcohol and ground, and grinding is uniform rearmounted The 500-600 in the tube furnace of oxygen atmosphereoAfter C pre-burnings 2-6h, 600-800 DEG C of calcining 8-15 h is warming up to, sandwich tape is obtained The spherical LiMn2O4 in hole；
（6）By graphene dispersion in deionized water, step is added（5）Obtained multilayer spherical LiMn2O4 with holes, stirring, from The heart is dried, and obtains graphene composite multi-layer spherical manganic acid lithium electrode material with holes.
The step（1）The mass ratio of middle cetyl trimethylammonium bromide, ammonium hydrogen carbonate and water is 1：（40-50）： 1000；The step（2）In manganese sulfate and water mass ratio be 1：80-100；The step（5）Presoma three aoxidize The mol ratio of two manganese and lithium salts is 8-10：1.
Lithium ion battery prepared by described graphene composite multi-layer spherical manganic acid lithium electrode material with holes, mainly by just Pole piece, negative plate, electrolyte, barrier film and shell are constituted, and lithium ion battery uses described graphene composite multi-layer class with holes Spherical lithium manganate electrode material as positive electrode, using lithium metal or can embedding de- lithium active material be used as negative material, barrier film For polyethylene, microporous polypropylene membrane, fibreglass diaphragm or their various composite diaphragms, soluble lithium salt organic solution is electricity Solve liquid.
Lithium ion battery negative material prepared by described graphene composite multi-layer spherical manganic acid lithium electrode material with holes For lithium metal or can embedding de- lithium active material, including carbon material or titanium base material and its composite.
The soluble lithium salt organic solution is dissolved in organic solvent for lithium salts to be obtained, and the lithium salts is lithium hexafluoro phosphate （LiPF6）, lithium perchlorate（LiClO4）, LiBF4（LiBF4）, hexafluoroarsenate lithium（LiAsF6）, trifluoromethyl sulfonic acid lithium （LiCF3SO3）, two (trimethyl fluoride sulfonyl) imine lithiums（LiN(CF3SO2)2）One or more, organic solvent is ethylene carbonate Ester（EC）, propene carbonate（PC）, dimethyl carbonate（DMC）, diethyl carbonate（DEC）, dimethyl ether（DME）And tetrahydrofuran （THF）In one or more.
The conductive agent of the lithium ion battery is acetylene black, carbon black or graphite, and binding agent is polytetrafluoroethylene (PTFE), polyvinylidene fluoride Alkene, sodium carboxymethylcellulose, polyacrylic acid or butadiene-styrene rubber, dispersant are water, ethanol, isopropanol or 1- methyl -2- pyrrolidines Ketone.
The positive plate and negative plate of described lithium ion battery are uniformly mixed using above conductive agent, binding agent and dispersant Slurry full-filling obtained by after conjunction is made on collector.
Described collector is carbon cloth, metal stainless steel, nickel, porous, the netted or thin-film material of aluminium.
The shell of described lithium ion battery uses organic plastics, aluminum hull, aluminum plastic film（Soft-package battery）, stainless steel and its multiple Condensation material.
The shape of described lithium ion battery can be button, column or square.
The beneficial effects of the invention are as follows：The advantage of the invention is that using graphene composite multi-layer spherical LiMn2O4 with holes It is used as positive electrode.1-5 μm of the material particle size, is formed by 100-200 nm primary particle accumulation, with it is porous, be layered, open Mouthful pattern, and graphene sheet layer even structure be dispersed in around LiMn2O4, electronics and ion in material can be significantly improved Diffusion rate, strengthens electrochemical stability, and then obtain high low cost, abundant raw material, voltage, good rate capability and stable circulation Property strong lithium ion battery, improve the power and energy density of material.It is inexpensive, safe, environment-friendly etc. excellent with reference to electrode material Point, comprising the material can charge and discharge lithium ion battery there is high-energy-density and high power density, applied with wide market Prospect.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing There is the accompanying drawing used required in technology description to be briefly described, it should be apparent that, drawings in the following description are only this Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the X-ray diffraction of multilayer spherical LiMn2O4 with holes prepared by embodiment 1（XRD）Figure.
Fig. 2 is the SEM of multilayer spherical LiMn2O4 with holes prepared by embodiment 1（SEM）Figure.
Fig. 3 is the SEM figures of graphene composite multi-layer spherical LiMn2O4 with holes prepared by embodiment 1.
Fig. 4 is lithium ion battery charging and discharging curve figure in embodiment 1.
Fig. 5 is lithium ion battery high rate performance figure in embodiment 1.
Fig. 6 is cycle performance of lithium ion battery figure in embodiment 1.
Fig. 7 is lithium ion battery charging and discharging curve figure in embodiment 2.
Fig. 8 is lithium ion battery charging and discharging curve figure in embodiment 3.
Fig. 9 is lithium ion battery charging and discharging curve figure in embodiment 4.
Figure 10 is lithium ion battery charging and discharging curve figure in embodiment 5.
Figure 11 is lithium ion battery charging and discharging curve figure in embodiment 6.
Figure 12 is lithium ion battery charging and discharging curve figure in embodiment 7.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not paid Embodiment, belongs to the scope of protection of the invention.
Embodiment 1
The synthesis step of graphene composite multi-layer spherical LiMn2O4 with holes used in the present invention is as follows：Weigh 0.25 g hexadecanes Base trimethylammonium bromide（CTAB）Mixed solution one is formed in 250 mL deionized waters with 11.85 g ammonium bicarbonate solubilities, separately Weigh 2.54 g manganese sulfates and be dissolved in formation mixed solution two in 250 mL deionized waters.By mixed solution two in 50 DEG C of oil bath After 30 min are added drop-wise in mixed solution one, regulation pH is 7.5, and constant pH keeps 30 min, obtained muddiness in oil bath Solution is after standing one day, and washing centrifugation is placed in 60 DEG C of drying in oven, obtains the primary powder of manganese carbonate.Primary powder is existed With 710 DEG C of calcinings in Muffle furnace, presoma manganese sesquioxide managnic oxide is obtained.Take 0.084 g LiOHH2O and 0.3 g tri- oxidations two Manganese is placed in mortar, using 1 mL absolute ethyl alcohols as solvent, after grinding is uniform, is transferred in porcelain cup, is placed in the pipe of oxygen atmosphere In formula stove with 560 DEG C of h of pre-burning 4 after, be warming up to 750 DEG C calcining 10 h, obtain multilayer spherical LiMn2O4 with holes.Afterwards, weigh 5 wt% graphene dispersion after ultrasonic 1 h, adds multilayer spherical mangaic acid lithium powder with holes, stirring in 50 mL deionized waters Centrifugal drying after 4 h, obtains the multilayer spherical LiMn2O4 with holes of composite graphite alkene.
Fig. 1 is multilayer spherical LiMn2O4 X-ray diffraction with holes（XRD）Figure, the standard card phase with spinel lithium manganate Correspondence, and crystallinity is good, Fig. 2 is multilayer spherical LiMn2O4 SEM with holes（SEM）Figure, LiMn2O4 is multilayer Spherical LiMn2O4 with holes, is the secondary structure being piled into by 100-200 nm little particle；Fig. 3 is after composite graphite alkene The SEM figures of multilayer spherical LiMn2O4 with holes, graphene is 1 μm or so of lamella particle, is dispersed in the particle of LiMn2O4 On.
It regard prepared graphene composite multi-layer spherical lithium manganate material with holes as positive electrode active materials, positive electrode With acetylene black, Kynoar with 80：10：10 mass ratioes are mixed, and use 1-Methyl-2-Pyrrolidone for dispersant, will be above-mentioned Mixture is well mixed to be tuned into slurry and is applied on aluminium foil, is cut out after 60 DEG C of drying and is obtained anode pole piece, lithium piece is negative pole（Negative pole holds Amount is much larger than cut out positive plate capacity）, anode pole piece and lithium piece are used to the polypropylene microporous of the models of Celgard 2500 Film is separated, and uses 1 M LiPF6It is dissolved in EC：DMC（Mass ratio is 1：1）For electrolyte, stainless steel box hat is assembled into as shell CR2016 formula button cells, the lithium ion battery that said process is assembled at room temperature, fills in 3.0 V-4.5 V potential range Discharge test, its charging and discharging curve, high rate performance and cycle performance are as shown in Figure 4, Figure 5 and Figure 6.Discharge platform is in 4 V under 1C Left and right, under 50 C multiplying power, its specific discharge capacity can reach that material is still protected after circulation in 400 weeks under 110 mAh/g, 10 C multiplying powers 114.7 mAh/g capacity is held.
Embodiment 2
The preparation be the same as Example 1 of the present embodiment graphene composite multi-layer spherical lithium manganate material with holes.
It regard prepared graphene composite multi-layer spherical lithium manganate material with holes as positive electrode active materials, commercial graphite As negative active core-shell material, positive pole and negative active core-shell material and acetylene black, Kynoar are with 80：10：10 mass ratioes are mixed, and are adopted It is dispersant with 1-Methyl-2-Pyrrolidone, is tuned into said mixture is well mixed slurry and is applied to respectively on aluminium foil and copper foil, 60 DEG C of drying obtain corresponding anode pole piece and cathode pole piece after cutting out（Capacity of negative plates holds much larger than cut out positive plate Amount）, pole piece is separated with lithium piece using the microporous polypropylene membrane of the models of Celgard 2500,1 M LiPF are used6It is dissolved in EC： DMC（Mass ratio is 1：1）For electrolyte, stainless steel box hat is assembled into CR2016 formula button cells, said process institute as shell The lithium ion battery of assembling at room temperature, carries out constant current charge-discharge test with 1 C multiplying powers in 2.8-4.5 V potential range, put Level platform is in 3.65 V or so, and test result shows that the specific discharge capacity of the battery is 113mAh/g, its charging and discharging curve such as Fig. 7 It is shown.
Embodiment 3
It regard the spherical lithium manganate material with holes of the graphene composite multi-layer prepared by embodiment 1 as positive electrode active materials, positive pole Material is with acetylene black, Kynoar with 80：10：10 mass ratioes are mixed, and use 1-Methyl-2-Pyrrolidone for dispersant, will Said mixture is well mixed to be tuned into slurry and is applied on aluminium foil, is cut out after 60 DEG C of drying and is obtained anode pole piece, lithium piece is negative pole （Capacity of negative plates is much larger than cut out positive plate capacity）, by anode pole piece and lithium piece using whatman fibreglass diaphragms every Open, use 1 MLiPF6It is dissolved in EC：DMC（Mass ratio is 1：1）For electrolyte, stainless steel box hat is assembled into as shell CR2025 formula button cells, the lithium ion battery that said process is assembled at room temperature, in 3.0 V-4.5 V potential range with 0.5 C multiplying powers carry out charge-discharge test.Test result shows that the specific discharge capacity of the battery is 135 mAh/g, and its discharge and recharge is bent Line is as shown in Figure 8.
Embodiment 4
It regard the spherical lithium manganate material with holes of the graphene composite multi-layer prepared by embodiment 1 as positive electrode active materials, positive pole Material is with acetylene black, Kynoar with 80：10：10 mass ratioes are mixed, and use 1-Methyl-2-Pyrrolidone for dispersant, will Said mixture is well mixed to be tuned into slurry and is applied on aluminium foil, is cut out after 60 DEG C of drying and is obtained anode pole piece, lithium piece is negative pole（It is negative Pole capacity is much larger than cut out positive plate capacity）, anode pole piece and lithium piece are used to the polypropylene of the models of Celgard 2500 Microporous barrier is separated, and uses 1 M LiPF6It is dissolved in EC, DMC, DEC solvent（FEC additives）For electrolyte, stainless steel box hat conduct Shell, is assembled into the formula button cells of CR 2025, the lithium ion battery that said process is assembled at room temperature, 3.0 V-4.5 V's Charge-discharge test is carried out with 0.5 C multiplying powers in potential range.Test result shows that the specific discharge capacity of the battery is 137.4mAh/ G, its charging and discharging curve is as shown in Figure 9.
Embodiment 5
It regard the spherical lithium manganate material with holes of the graphene composite multi-layer prepared by embodiment 1 as positive electrode active materials, positive pole Material is with acetylene black, sodium carboxymethylcellulose with 80：10：10 mass ratioes are mixed, and adopt water as dispersant, said mixture is mixed Conjunction is uniformly tuned into slurry and is applied on aluminium foil, is cut out after 60 DEG C of drying and obtains anode pole piece, lithium piece is negative pole（Capacity of negative plates is long-range In the positive plate capacity cut out）, anode pole piece is separated with lithium piece using the microporous polypropylene membrane of Celgard models, 1 is used M LiPF6It is dissolved in EC：DMC（Mass ratio is 1：1）For electrolyte, stainless steel box hat is assembled into the formula buttons of CR 2025 as shell Battery, the lithium ion battery that said process is assembled at room temperature, is entered in 3.0 V-4.5 V potential range with 0.5 C multiplying powers Row charge-discharge test.Test result shows that the specific discharge capacity of the battery is 132.4 mAh/g, its charging and discharging curve such as Figure 10 institutes Show.
Embodiment 6
It regard the spherical lithium manganate material with holes of the graphene composite multi-layer prepared by embodiment 1 as positive electrode active materials, business Graphite is as negative active core-shell material, and positive pole and negative active core-shell material and acetylene black, Kynoar are with 80：10：10 mass ratioes are mixed Close, use 1-Methyl-2-Pyrrolidone for dispersant, said mixture is well mixed and is tuned into slurry and is applied to aluminium foil and copper respectively On paper tinsel, 60 DEG C of drying obtain corresponding anode pole piece and cathode pole piece after cutting out（Capacity of negative plates is much larger than cut out positive plate Capacity）, pole piece is separated with lithium piece using the microporous polypropylene membrane of the models of Celgard 2500,1 M bis- is used（Trifluoromethyl Sulphonyl）Imine lithium is dissolved in EC：DMC（Mass ratio is 1：1）For electrolyte, stainless steel box hat is assembled into CR2025 formulas as shell Button cell, at room temperature, 2.8 V-4.5 V potential range is interior with 1 C multiplying powers for the lithium ion battery that said process is assembled Constant current charge-discharge test is carried out, discharge platform is in 3.65 V or so, and test result shows that the specific discharge capacity of the battery is 113mAh/g, its charging and discharging curve is as shown in figure 11.
Embodiment 7
It regard the spherical lithium manganate material with holes of the graphene composite multi-layer prepared by embodiment 1 as positive electrode active materials, metatitanic acid Lithium is as negative active core-shell material, and positive pole and negative active core-shell material and acetylene black, Kynoar are with 80：10：10 mass ratioes are mixed, 1-Methyl-2-Pyrrolidone is used for dispersant, slurry is tuned into said mixture is well mixed and is applied to aluminium foil and copper foil respectively On, 60 DEG C of drying obtain corresponding anode pole piece and cathode pole piece after cutting out（Capacity of negative plates holds much larger than cut out positive plate Amount）, pole piece is separated with lithium piece using the microporous polypropylene membrane of the models of Celgard 2500,1 M trifluoromethyl sulfonic acid lithiums are used It is dissolved in EC：DMC（Mass ratio is 1：1）For electrolyte, stainless steel box hat is assembled into CR2025 formula button cells as shell, on The lithium ion battery that the process of stating is assembled carries out constant current with 0.5 C multiplying powers at room temperature, in 1.5 V-3.0 V potential range and filled Discharge test, discharge platform is mainly in 2.4-2.7 V, and test result shows that the specific discharge capacity of the battery is 104 mAh/g, its Charging and discharging curve is as shown in figure 12.
Embodiment 8
Spherical lithium manganate electrode material particle diameter is 1 μm in the present embodiment.
The amount of graphene is the 10% of spherical lithium manganate quality in manganic acid lithium electrode material.
The preparation method of manganic acid lithium electrode material is as follows：
（1）0.25g cetyl trimethylammonium bromides and 11.25g ammonium bicarbonate solubilities are formed mixed in 250ml deionized waters Close solution one；
（2）2.54g manganese sulfates are dissolved in formation mixed solution two in 241.3g deionized waters；
（3）By step（1）Obtained mixed solution one is placed in 50 DEG C of oil bath, by step（2）The obtained drop of mixed solution two It is added in mixed solution one, time for adding is that regulation pH is 7.5 after 30min, completion of dropping, and 30min is kept in oil bath, is obtained Turbid solution；
（4）By step（3）Obtained turbid solution stands and centrifugation is washed after 24h, and in being dried at 60-80 DEG C, obtains manganese carbonate Primary powder, manganese carbonate primary powder is calcined at 730 DEG C, obtains presoma manganese sesquioxide managnic oxide；
（5）By step（4）Obtained 0.35g presomas manganese sesquioxide managnic oxide and 0.1g lithium perchlorates is added in 1ml absolute ethyl alcohols Grinding, is placed in the tube furnace of oxygen atmosphere after 560 DEG C of pre-burning 4h, to be warming up to 750 DEG C of calcining 10h after grinding is uniform, obtains Multilayer spherical LiMn2O4 with holes；
（6）By graphene dispersion ultrasonic 1 h in deionized water, step is added（5）Obtained multilayer spherical LiMn2O4 with holes, Centrifugal drying after 4 h is stirred, manganic acid lithium electrode material is obtained.
By the use of manganic acid lithium electrode material manufactured in the present embodiment as positive electrode, with can the carbon material of embedding lithium ionic insertion/deinsertion make For negative material, positive electrode is with carbon black, sodium carboxymethylcellulose using mass ratio as 80:10:10 mixing, it is scattered to use ethanol Agent；It is tuned into said mixture is well mixed slurry and is applied on carbon cloth, is cut out after 60 DEG C of drying and obtain anode pole piece.By positive pole Pole piece uses polyethylene with lithium piece（PE）Microporous barrier is separated.
Lithium perchlorate is dissolved in dimethyl carbonate and diethyl carbonate（1:1）In prepare electrolyte, organic plastics is as outer Shell, prepares lithium ion battery.
Embodiment 9
Spherical lithium manganate electrode material particle diameter is 2 μm in the present embodiment.
The amount of graphene is the 20% of spherical lithium manganate quality in manganic acid lithium electrode material.
The preparation method of manganic acid lithium electrode material is as follows：
（1）0.25g cetyl trimethylammonium bromides and 10g ammonium bicarbonate solubilities are formed into mixing in 250ml deionized waters Solution one；
（2）2.54g manganese sulfates are dissolved in formation mixed solution two in 228.6g deionized waters；
（3）By step（1）Obtained mixed solution one is placed in 50 DEG C of oil bath, by step（2）The obtained drop of mixed solution two It is added in mixed solution one, time for adding is that regulation pH is 7 after 30min, completion of dropping, and 30min is kept in oil bath, is mixed Turbid solution；
（4）By step（3）Obtained turbid solution stands and centrifugation is washed after 24h, and in being dried at 60-80 DEG C, obtains manganese carbonate Calcined at primary powder, manganese carbonate 800 DEG C of powder of primary, obtain presoma manganese sesquioxide managnic oxide；
（5）By step（4）Obtained 0.4g presomas manganese sesquioxide managnic oxide and 0.1g LiBF4s is added in 1ml absolute ethyl alcohols Grinding, is placed in the tube furnace of oxygen atmosphere after 500 DEG C of pre-burning 6h, to be warming up to 800 DEG C of calcining 8h after grinding is uniform, obtains many Layer spherical LiMn2O4 with holes；
（6）Graphene slurry is dissolved in ultrasonic 1 h in deionized water, step is added（5）Obtained multilayer spherical mangaic acid with holes Centrifugal drying after lithium, 4 h of stirring, obtains manganic acid lithium electrode material.
By the use of manganic acid lithium electrode material manufactured in the present embodiment as positive electrode, with can embedding lithium ionic insertion/deinsertion titanium base material As negative material, positive electrode is with graphite and Kynoar using mass ratio as 80:10:10 mixing, use isopropanol to divide Powder；It is tuned into said mixture is well mixed slurry and is applied on the porous material of aluminium, is cut out after 60 DEG C of drying and obtain positive pole pole Piece.Anode pole piece and lithium piece are used into polyimide film（PI）Barrier film is separated.
LiBF4 is dissolved in dimethyl carbonate, diethyl carbonate and tetrahydrofuran and prepares electrolyte, aluminum hull conduct Shell, prepares lithium ion battery.
Embodiment 10
Spherical lithium manganate electrode material particle diameter is 5 μm in the present embodiment.
The amount of graphene is the 1% of spherical lithium manganate quality in manganic acid lithium electrode material.
The preparation method of manganic acid lithium electrode material is as follows：
（1）0.25g cetyl trimethylammonium bromides and 10g ammonium bicarbonate solubilities are formed into mixing in 250ml deionized waters Solution one；
（2）2.54g manganese sulfates are dissolved in formation mixed solution two in 228.6g deionized waters；
（3）By step（1）Obtained mixed solution one is placed in 50 DEG C of oil bath, by step（2）The obtained drop of mixed solution two It is added in mixed solution one, time for adding is that regulation pH is 8 after 30min, completion of dropping, and 30min is kept in oil bath, is mixed Turbid solution；
（4）By step（3）Obtained turbid solution stands and centrifugation is washed after 24h, and in being dried at 60-80 DEG C, obtains manganese carbonate Primary powder, manganese carbonate primary powder is calcined at 600 DEG C, obtains presoma manganese sesquioxide managnic oxide；
（5）By step（4）Obtained 0.3g presomas manganese sesquioxide managnic oxide and 0.1g hexafluoroarsenate lithiums is added in 1ml absolute ethyl alcohols Grinding, is placed in the tube furnace of oxygen atmosphere after 600 DEG C of pre-burning 2h, to be warming up to 600 DEG C of calcining 15h after grinding is uniform, obtains Multilayer spherical LiMn2O4 with holes；
（6）Ultrasonic 1 h in deionized water is dispersed graphene in, step is added（5）Obtained multilayer spherical LiMn2O4 with holes, Centrifugal drying after 4 h is stirred, manganic acid lithium electrode material is obtained.
By the use of manganic acid lithium electrode material manufactured in the present embodiment as positive electrode, with can embedding lithium ionic insertion/deinsertion carbon material and The composite of titanium base material is as negative material, and positive electrode is with carbon black and polytetrafluoroethylene (PTFE) using mass ratio as 80:10:10 mix Close, use isopropanol for dispersant；It is tuned into said mixture is well mixed slurry and is applied on the Web materials of aluminium, 60 DEG C of bakings Cut out after dry and obtain anode pole piece.Anode pole piece and lithium piece are used into polypropylene（PP）Microporous barrier is separated.
Lithium perchlorate is dissolved in ethylene carbonate and tetrahydrofuran（1:1）Electrolyte is prepared, aluminum hull is prepared as shell Lithium ion battery.
Embodiment 11
The preparation method be the same as Example 1 of spherical lithium manganate electrode material in the present embodiment.
Positive electrode, using lithium piece as negative material, positive pole are used as by the use of manganic acid lithium electrode material manufactured in the present embodiment Material is with acetylene black, polyacrylic acid using mass ratio as 80:10:10 mixing, using isopropanol dispersant；Said mixture is mixed Uniformly it is tuned into slurry to be applied on the thin-film material of nickel, is cut out after 60 DEG C of drying and obtain anode pole piece.Anode pole piece is adopted with lithium piece Use polypropylene（PP）Microporous barrier is separated.
By two（Trimethyl fluoride sulfonyl）Imine lithium is dissolved in diethyl carbonate, dimethyl ether and tetrahydrofuran（Three's volume ratio is 1:1:1）In prepare electrolyte, organic plastics prepares lithium ion battery as shell.
Embodiment 12
The preparation method be the same as Example 1 of spherical lithium manganate electrode material in the present embodiment.
Positive electrode, using lithium piece as negative material, positive pole are used as by the use of manganic acid lithium electrode material manufactured in the present embodiment Material is with graphite, polytetrafluoroethylene (PTFE) using mass ratio as 80:10:10 mixing, use 1-Methyl-2-Pyrrolidone for dispersant；Will Said mixture is well mixed to be tuned into slurry and is applied on metal stainless steel material, is cut out after 60 DEG C of drying and is obtained anode pole piece.Will Anode pole piece is separated with lithium piece using fibreglass diaphragm.
Trifluoromethyl sulfonic acid lithium is dissolved in diethyl carbonate, dimethyl ether and tetrahydrofuran and prepares electrolyte, stainless steel and Its composite prepares lithium ion battery as shell.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention God is with principle, and any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.

Claims (10)

1. a kind of graphene composite multi-layer spherical manganic acid lithium electrode material with holes, it is characterised in that：Graphene composite multi-layer band The spherical manganic acid lithium electrode material in hole is dispersed in around lithium manganate particle by the graphene uniform of lamellar structure to be constituted, the mangaic acid Lithium is the multilayer spherical structure with holes that primary particle is accumulated, and the particle diameter of primary particle is 100-200 nm, and accumulation is formed Multilayer spherical manganic acid lithium electrode material with holes particle diameter be 1-5 μm.
2. graphene composite multi-layer spherical manganic acid lithium electrode material with holes according to claim 1, it is characterised in that：Stone The amount of graphene is the 1%-20% of LiMn2O4 quality in black alkene composite multi-layer spherical manganic acid lithium electrode material with holes.
3. graphene composite multi-layer spherical manganic acid lithium electrode material with holes according to claim 1 or 2, its feature exists In the preparation method of the graphene composite multi-layer spherical manganic acid lithium electrode material with holes is as follows：
（1）Cetyl trimethylammonium bromide and ammonium bicarbonate solubility are formed into mixed solution one in deionized water；
（2）Manganese sulfate is dissolved in formation mixed solution two in deionized water；
（3）By step（1）Obtained mixed solution one is placed in 40-60 DEG C of oil bath, by step（2）Obtained mixed solution two It is added drop-wise in mixed solution one, pH is adjusted after completion of dropping between 7-8, to obtain turbid solution；
（4）By step（3）Obtained turbid solution washing centrifugation, drying obtains the primary powder of manganese carbonate, manganese carbonate primary powder Calcined at 600-800 DEG C, obtain presoma manganese sesquioxide managnic oxide；
（5）By step（4）Obtained presoma manganese sesquioxide managnic oxide and lithium salts is added in absolute ethyl alcohol and ground, and grinding is uniform rearmounted In the tube furnace of oxygen atmosphere after 500-600 DEG C of pre-burning 2-6h, 600-800 DEG C of calcining 8-15 h is warming up to, sandwich tape is obtained The spherical LiMn2O4 in hole；
（6）By graphene dispersion in deionized water, step is added（5）Obtained multilayer spherical LiMn2O4 with holes, stirring, from The heart is dried, and obtains graphene composite multi-layer spherical manganic acid lithium electrode material with holes.
4. graphene composite multi-layer spherical manganic acid lithium electrode material with holes according to claim 3, it is characterised in that：Institute State step（1）The mass ratio of middle cetyl trimethylammonium bromide, ammonium hydrogen carbonate and deionized water is 1：（40-50）：1000；Step Suddenly（2）Middle manganese sulfate and the mass ratio of deionized water are 1：（80-100）；The step（5）Presoma manganese sesquioxide managnic oxide and lithium The mol ratio of salt is（8-10）：1.
5. lithium ion battery prepared by the graphene composite multi-layer spherical manganic acid lithium electrode material with holes described in claim 1, It is made up of positive plate, negative plate, electrolyte, barrier film and shell, it is characterised in that：Lithium ion battery uses described graphene Composite multi-layer spherical manganic acid lithium electrode material with holes is as positive electrode, using lithium metal or can embedding de- lithium active material conduct Negative material, barrier film is polyethylene, microporous polypropylene membrane, fibreglass diaphragm or their various composite diaphragms, soluble lithium Salt organic solution is electrolyte.
6. lithium-ion electric prepared by graphene composite multi-layer spherical manganic acid lithium electrode material with holes according to claim 5 Pond, it is characterised in that：The positive plate and negative plate by positive electrode and negative material and conductive agent, binding agent and divide respectively Powder uniformly after mixing obtained by slurry full-filling obtained to collector, collector is carbon cloth, metal stainless steel, nickel and aluminium Porous, netted or thin-film material.
7. lithium-ion electric prepared by graphene composite multi-layer spherical manganic acid lithium electrode material with holes according to claim 5 Pond, it is characterised in that：It is described can embedding de- lithium active material for can embedding lithium ionic insertion/deinsertion carbon material or titanium base material, or for can The carbon material of embedding lithium ionic insertion/deinsertion and the composite of titanium base material.
8. lithium-ion electric prepared by graphene composite multi-layer spherical manganic acid lithium electrode material with holes according to claim 5 Pond, it is characterised in that：Described conductive agent is acetylene black, carbon black or graphite；Binding agent be polytetrafluoroethylene (PTFE), Kynoar, Sodium carboxymethylcellulose, polyacrylic acid or butadiene-styrene rubber；Dispersant is water, ethanol, isopropanol or 1-Methyl-2-Pyrrolidone.
9. lithium-ion electric prepared by graphene composite multi-layer spherical manganic acid lithium electrode material with holes according to claim 5 Pond, it is characterised in that：The soluble lithium salt organic solution is dissolved in organic solvent for lithium salts to be obtained, and the lithium salts is hexafluoro phosphorus Sour lithium, lithium perchlorate, LiBF4, hexafluoroarsenate lithium, trifluoromethyl sulfonic acid lithium and two（Trimethyl fluoride sulfonyl）Imine lithium One or more, organic solvent is ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, dimethyl ether and tetrahydrochysene One or more in furans.
10. lithium ion prepared by graphene composite multi-layer spherical manganic acid lithium electrode material with holes according to claim 5 Battery, it is characterised in that：Described shell uses organic plastics, aluminum hull, aluminum plastic film, stainless steel and its composite, is shaped as Button, column or square.
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CN108448092A (en) * 2018-03-20 2018-08-24 桂林理工大学 A kind of preparation method with high rate capability and cycle performance LiMn2O4/three-dimensional graphene composite material
CN108847481A (en) * 2018-06-29 2018-11-20 华南师范大学 A kind of preparation and application of the porous manganese sesquioxide managnic oxide cube negative electrode material of high performance lithium ion battery carbon coating
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CN110176595A (en) * 2019-06-06 2019-08-27 电子科技大学 A kind of anode material for lithium-ion batteries LiMnO2@C and preparation method thereof
CN110190277A (en) * 2019-06-06 2019-08-30 电子科技大学 A kind of anode material for lithium-ion batteries LiMnO2@C and preparation method thereof
CN110190277B (en) * 2019-06-06 2022-05-03 电子科技大学 Lithium ion battery anode material LiMnO2@ C and preparation method thereof
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CN111239222A (en) * 2020-01-16 2020-06-05 郑州大学 Ionic liquid electrolyte and electrochemical gas sensor
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CN114094061A (en) * 2021-10-09 2022-02-25 温州大学 Rice-grain-shaped manganese carbonate composite graphene high-performance lithium storage material and lithium battery
CN114094061B (en) * 2021-10-09 2024-06-04 温州大学 Rice grain-shaped manganese carbonate composite graphene high-performance lithium storage material and lithium battery

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