CN110504411A - Preparation method, lithium ion cell positive, lithium ion battery and the electric device of lithium ion cell positive - Google Patents
Preparation method, lithium ion cell positive, lithium ion battery and the electric device of lithium ion cell positive Download PDFInfo
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- CN110504411A CN110504411A CN201910815434.XA CN201910815434A CN110504411A CN 110504411 A CN110504411 A CN 110504411A CN 201910815434 A CN201910815434 A CN 201910815434A CN 110504411 A CN110504411 A CN 110504411A
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- 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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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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Abstract
The present invention provides a kind of preparation method of lithium ion cell positive, lithium ion cell positive, lithium ion battery and electric devices, are related to technical field of lithium ion.The preparation method of the lithium ion cell positive, the high price Mn being effectively utilized in graphene preparation process7+Ion realizes the higher value application of raw material;Simultaneously, above-mentioned growth in situ process, which also ensures to be formed by, has excellent uniformity and film forming with graphene/LiMn2O4 composite construction lithium ion cell positive, it is applied in lithium ion battery, can effectively promotes the energy density and cyclical stability of lithium ion battery;In addition, the preparation method, simple process operate conveniently, repeatability is high, provides foundation for industrial production.The present invention also provides using lithium ion cell positive made from above-mentioned preparation method, which is the membrane electrode structure for exempting from collector and bonding agent, and the energy density and cyclical stability of battery entirety can be improved.
Description
Technical field
The present invention relates to technical field of lithium ion, preparation method, lithium in particular to lithium ion cell positive
Ion battery anode, lithium ion battery and electric device.
Background technique
The energy is that material base is wanted in developing national economy and the life uplifted the people's living standard, and directly affects economic hair
One key factor of exhibition.Since the 21th century, shortage of resources, environmental pollution brought by traditional energy utilization patterns,
The problems such as greenhouse effects, becomes increasingly conspicuous, and improves energy resource structure, develops efficient, clean new energy and has become global common recognition.Lithium
Ion battery receives the blueness of people due to superior performances such as its is safe and environment-friendly, high-energy-density and good chemical properties
It looks at.For energy miniaturization and the emerging integrated requirement of composite energy storage system, the lithium-ion electric for meeting traditional microelectronic device
Pond is further development of film lithium ion battery ultra-thin, flexible, with high-energy density.
The Chinese patent of Patent No. CN200410018330.X reports a kind of use electrostatic spray deposition precursor body, after
High-temperature process prepares lithium-transition metal phosphate nano thin-film method of olivine structural, and lithium is uniformly mixed in alcoholic solvent
Salt precursor body mixing P2O5Spraying at presoma, 700 DEG C of calcinings are prepared for anode thin film under an inert atmosphere, have certain follow
Ring performance.Although this method can prepare nano thin-film, subsequent high-temperature process limits the use of collector, so that
Conventional aluminum metal collector (660 DEG C of fusing point) can not be applied in hull cell.In addition, this film cycle performance usually compared with
Difference does not have long circulating performance.
Document report (Journal of Alloys and Compounds, 2017,713:64-68), Suat Pat et al.
Li is prepared for using the method for magnetron sputtering4Ti5O12And LiFePO4Film is assembled into full battery, has certain cycle performance.
Vapour deposition process such as magnetron sputtering, atomic layer deposition etc. are a kind of conventional film means, and this method is available uniform
Film, but it is constrained to equipment, finite thickness can destroy simultaneously because being the process recrystallized in film forming procedure
The crystal structure of material itself, needs subsequent high temperature to make annealing treatment, and is equally encountered by the problem of conventional collector is not available.
In view of this, the present invention is specifically proposed at least one of to solve the above technical problems.
Summary of the invention
The first purpose of this invention is to provide a kind of preparation method of lithium ion cell positive, is effectively utilized graphite
High price Mn in alkene preparation process7+Ion realizes the higher value application of raw material;Meanwhile above-mentioned growth in situ process is also protected
It has demonstrate,proved to be formed by and there is excellent uniformity and film forming with graphene/LiMn2O4 composite construction lithium ion cell positive
Property.
Second object of the present invention is to provide a kind of lithium ion cell positive, using above-mentioned lithium ion cell positive
Preparation method is prepared.
Third object of the present invention is to provide a kind of lithium ion battery, includes above-mentioned lithium ion cell positive or use
Lithium ion cell positive made from the preparation method of above-mentioned lithium ion cell positive.
Fourth object of the present invention is to provide a kind of electric device of above-mentioned lithium ion battery.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
The present invention provides a kind of lithium ion cell positives, include the following steps;
(a) graphite, potassium permanganate and mixed acid are mixed, water and hydrogen peroxide is added in reaction after reaction, the reaction was continued, obtains
To the first mixed solution;
(b) reducing substances are mixed with the first mixed solution, carries out hydro-thermal reaction, after the drying of obtained hydrothermal product
It is mixed with the solution containing lithium source, obtains the second mixed solution;
(c) the second mixed solution is subjected to hydro-thermal reaction, disperses obtained hydrothermal product in solvent, film is made,
Obtain lithium ion cell positive.
Further, on technical solution of the present invention basis, in step (a), the graphite includes crystalline flake graphite, swollen
In swollen graphite, graphite oxide or thermal cracking graphite any one or at least two combination, preferably crystalline flake graphite;
And/or in step (a), the granularity of the graphite is 50-200 mesh;
And/or in step (a), the mixed acid includes sulfuric acid and phosphoric acid, and the volume ratio of sulfuric acid and phosphoric acid is (3-7): 1;
And/or in step (a), the mass ratio of the graphite, potassium permanganate and mixed acid is (0.16-0.5): (1-3):
(40-72);
And/or in step (a), the temperature of the reaction is 40-50 DEG C, and the time of the reaction is 10-15h.
Further, on technical solution of the present invention basis, in step (b), the reducing substances are to contain NH4+
Reproducibility alkaline matter, preferably include ethylenediamine and/or hydrazine hydrate;
And/or in step (b), the dosage of the reducing substances of addition is to make the pH value of first mixed solution
Reach neutrality;
And/or in step (b), the temperature of the hydro-thermal reaction is 100-140 DEG C, and the time of the hydro-thermal reaction is 10-
24h;
And/or in step (b), the drying is freeze-drying;
And/or in step (b), the lithium source includes any one in lithium hydroxide, lithium nitrate, lithium carbonate or lithium acetate
Kind or at least two combination.
Further, on technical solution of the present invention basis, in step (c), the temperature of the hydro-thermal reaction is
200-260 DEG C, the time of the hydro-thermal reaction is 18-36h;
And/or in step (c), the solvent includes any one or at least two in ethyl alcohol, ethylene glycol or glycerine
The combination of kind.
Further, on technical solution of the present invention basis, in step (b), the hydro-thermal reaction is in polytetrafluoroethyl-ne
It is carried out in alkene reaction container, the mixed liquor that the reducing substances and the first mixed solution are formed is in polytetrafluoroethylene (PTFE) reaction vessel
In packing ratio be 1/2-2/3;
And/or in step (c), the hydro-thermal reaction carries out in polytetrafluoroethylene (PTFE) reaction vessel, and second mixing is molten
Packing ratio of the liquid in polytetrafluoroethylene (PTFE) reaction vessel is 1/2-2/3.
Further, technical solution of the present invention basis on, in step (c), the film with a thickness of 2-10 μm.
Further, on technical solution of the present invention basis, the lithium ion cell positive is formed in for LiMn2O4
The membrane structure of graphene between layers, and the lithium ion cell positive does not include collector and bonding agent.
The present invention also provides a kind of lithium ion cell positives, are prepared using the preparation method of above-mentioned lithium ion cell positive
It obtains;
The lithium ion cell positive is that LiMn2O4 is formed in the membrane structure of graphene between layers, and the lithium from
Sub- anode does not include collector and bonding agent.
The present invention also provides a kind of lithium ion batteries, include above-mentioned lithium ion cell positive.
The present invention also provides a kind of electric devices, include above-mentioned lithium ion battery.
Compared with prior art, the preparation method of lithium ion cell positive provided by the invention, lithium ion cell positive and
Lithium ion battery has the advantage that
(1) the present invention provides a kind of preparation methods of lithium ion cell positive, first in graphene preparation process
High price Mn7+Ion is reduced to after lower valency with Mn (OH)2Form in-situ deposition graphene oxide between layers,
Then graphene oxide is restored by hydro-thermal method, is aoxidized by dry by Mn (OH)2It is converted into embeddable lithium ion
Mn3O4Structure then carries out embedding lithium preparation again, and forming structure is that LiMn2O4 is adsorbed on the lithium-ion electric of graphene between layers
Pond anode.Above-mentioned preparation method, the high price Mn being effectively utilized in graphene preparation process7+Ion realizes the high level of raw material
Change and utilizes;Meanwhile above-mentioned growth in situ process also ensure be formed by with graphene/LiMn2O4 composite construction lithium from
Sub- anode has excellent uniformity and film forming, is applied in lithium ion battery, can effectively promote lithium-ion electric
The energy density and cyclical stability in pond;
In addition, the preparation method of lithium ion cell positive provided by the invention, simple process operate conveniently, process stabilizing
Property it is strong, repeatability is high, provides foundation for industrial production.
(2) the present invention provides a kind of lithium ion cell positive, which is to exempt from collector and bonding agent
Membrane electrode structure, can be improved the energy density of battery entirety, and using limited will not influence it due to collector and answer
With;Meanwhile the lithium ion cell positive can effectively inhibit bulk effect of anode during lithium ion deintercalation, keep electricity
Pole integrality improves the cycle life of battery.
(3) the present invention provides a kind of lithium ion batteries, include above-mentioned lithium ion cell positive.In view of above-mentioned lithium-ion electric
Advantage possessed by the anode of pond, so that lithium ion battery energy density with higher and longer cycle life.
(4) the present invention also provides a kind of electric devices, include above-mentioned lithium ion battery.In view of above-mentioned lithium ion battery institute
It has the advantage that, so that the electric device comprising above-mentioned lithium ion battery can also obtain identical effect.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the SEM figure for the lithium ion cell positive that the embodiment of the present invention 1 provides;
Fig. 2 is the cycle performance figure of the lithium ion battery of the lithium ion cell positive provided using the embodiment of the present invention 1.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
It should be understood that in the present invention, if without particularly illustrating, all embodiments mentioned in this article and
Preferred implementation method can be combined with each other to form new technical solution.
In the present invention, if without particularly illustrating, all technical characteristics and preferred feature mentioned in this article can be with
Intercombination forms new technical solution.
In the present invention, if percentage (%) or part refer to the weight relative to composition without particularly illustrating
Percentage or parts by weight.
In the present invention, if related each component or its preferred ingredient can be combined with each other shape without particularly illustrating
The technical solution of Cheng Xin.
In the present invention, unless otherwise indicated, numberical range " a~b " indicates the contracting of any real combinings between a to b
Sketch form shows that wherein a and b is real number.Such as numberical range " 6~22 " indicate herein all listed " 6~22 " it
Between whole real numbers, " 6~22 " be these combinations of values breviary indicate.
" range " disclosed in this invention can be respectively one or more lower limits and one in the form of lower and upper limit
A or multiple upper limits.
In the present invention, unless otherwise indicated, it is each reaction or operating procedure can sequentially carry out, can also in sequence into
Row.Preferably, reaction method herein is that sequence carries out.
Unless otherwise indicated, profession used herein and meaning phase known to scientific term and one skilled in the art
Together.In addition, any method similar to or equal to what is recorded or material can also be applied in the present invention.
According to an aspect of the invention, there is provided lithium ion cell positive, includes the following steps;
(a) graphite, potassium permanganate and mixed acid are mixed, water and hydrogen peroxide is added in reaction after reaction, the reaction was continued, obtains
To the first mixed solution;
(b) reducing substances are mixed with the first mixed solution, carries out hydro-thermal reaction, after the drying of obtained hydrothermal product
It is mixed with the solution containing lithium source, obtains the second mixed solution;
(c) the second mixed solution is subjected to hydro-thermal reaction, disperses obtained hydrothermal product in solvent, film is made,
Obtain lithium ion cell positive.
In the present invention, step (a) mainly utilizes the raw materials such as graphite, potassium permanganate, mixed acid and hydrogen peroxide by graphite
The main component being made in graphene oxide, that is, the first mixed solution is graphene oxide.
In addition to graphene oxide, there is also have potassium permanganate in the first mixed solution.Reducing substances are utilized in step (b)
The pH value for adjusting the first mixed solution reaches neutrality, and simultaneously by the Mn in potassium permanganate7+Reduction obtains manganous hydroxide, raw
At manganous hydroxide be then adsorbed between graphene oxide layer and layer.Then hydro-thermal reaction is carried out, so that graphene oxide occurs
Reduction forms graphene, that is, forms manganous hydroxide and be adsorbed on the structure of graphene between layers.By obtained hydrothermal product into
Row drying, so that manganous hydroxide is dehydrated the Mn to form embeddable lithium ion3O4Structure.
In step (c), mixed after the hydrothermal product that step (b) obtains is dried with second of the solution formation containing lithium source
Solution carries out hydro-thermal reaction, so that being located at the Mn of graphene between layers3O4It reacts with lithium source and generates LiMn2O4, is i.e. shape
Graphene/LiMn2O4 the composite material (hydrolysate) of graphene between layers is adsorbed at LiMn2O4.Then hydrolysis is produced
Object is scattered in solvent, and film is made, and is formed membrane electrode, is obtained lithium ion cell positive.
The preparation method of lithium ion cell positive provided by the invention, first with the high price in graphene preparation process
Mn7+Ion is reduced to after lower valency with Mn (OH)2Form in-situ deposition graphene oxide between layers, then lead to
It crosses hydro-thermal method to restore graphene oxide, be aoxidized by dry by Mn (OH)2It is converted into the Mn of embeddable lithium ion3O4Knot
Structure then carries out embedding lithium preparation again, and forming structure is that LiMn2O4 is adsorbed on the lithium ion cell positive of graphene between layers.
Above-mentioned preparation method, the high price Mn being effectively utilized in graphene preparation process7+Ion realizes the higher value application of raw material;
Meanwhile above-mentioned growth in situ process also ensures and is formed by graphene/LiMn2O4 composite material lithium ion cell positive
With excellent uniformity and film forming, it is applied in lithium ion battery, the energy that can effectively promote lithium ion battery is close
Degree and cyclical stability.
In addition, the preparation method of lithium ion cell positive provided by the invention, simple process operate conveniently, process stabilizing
Property it is strong, repeatability is high, provides foundation for industrial production.
Specifically, during preparing graphene, the type of used graphite can there are many.As of the invention
A kind of optional embodiment, in step (a), graphite includes in crystalline flake graphite, expanded graphite, graphite oxide or thermal cracking graphite
Any one or at least two combination, preferably crystalline flake graphite.
Also there is certain restriction for the partial size of graphite.As a kind of optional embodiment of the invention, in step (a),
The granularity of graphite is 50-200 mesh, the granularity of typical but non-limiting graphite be 50 mesh, 60 mesh, 80 mesh, 100 mesh, 120 mesh,
150 mesh, 180 mesh or 200 mesh.
If graphite particle size is too small, continuous system can not be formed during aoxidizing removing, or even in the form of carbon dots
In the presence of;If graphite particle size is excessive, not fully strip, the graphene conductive of preparation is poor, therefore the granularity Ying Shi of graphite
In suitable range.
As a kind of optional embodiment of the invention, in step (a), mixed acid includes sulfuric acid and phosphoric acid, sulfuric acid and phosphorus
The volume ratio of acid is (3-7): 1, sulfuric acid and the typical but non-limiting volume ratio of phosphoric acid are 3:1,4:1,5:1,6:1 or 7:1.In
Big calorimetric can be discharged during mixed acid is added, reaction easily causes acid solution to splash under room temperature, therefore when mixed acid stirring is added
Keep ice bath environment.
As a kind of optional embodiment of the invention, in step (a), the mass ratio of graphite, potassium permanganate and mixed acid
For (0.16-0.5): (1-3): (40-72);The mass ratio of typical but non-limiting graphite, potassium permanganate and mixed acid is
0.16:1:40、0.2:1:40、0.3:1:50、0.5:1:70、0.16:2:40、0.16:3:50、0.16:1:60、0.2:1:72、
0.3:2:72,0.5:3:72,0.4:3:72 or 0.5:3:60.By the restriction to graphite, potassium permanganate and mixed acid dosage, make
Obtaining graphite may be implemented adequately to aoxidize.
As a kind of optional embodiment of the invention, in step (a), the temperature of reaction is 40-50 DEG C, the time of reaction
For 10-15h.The temperature of typical but non-limiting reaction is 40 DEG C, 42 DEG C, 44 DEG C, 45 DEG C, 46 DEG C, 48 DEG C or 50 DEG C, typical
But the time of unrestricted reaction is 10h, 11h, 12h, 13h, 14h or 15h.
As a kind of optional embodiment of the invention, in step (b), reducing substances are to contain NH4+Reproducibility alkali
Property substance, preferably includes ethylenediamine and/or hydrazine hydrate;
The pH value of the first mixed solution can be adjusted to neutrality using reducing substances, due to KMnO4In Mn7+In high price
State, to obtain to need to carry out reduction neutralization to it with the layer structure of removal lithium embedded containing manganese compound.
The dosage of reducing substances need to be determined according to the first mixed solution.As a kind of optional embodiment party of the invention
Formula, in step (b), the dosage of the reducing substances of addition is that the pH value of the first mixed solution is made to reach neutrality.
As a kind of optional embodiment of the invention, in step (b), the temperature of hydro-thermal reaction is 100-140 DEG C, hydro-thermal
The time of reaction is 10-24h;The temperature of typical but non-limiting hydro-thermal reaction be 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C,
120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C or 140 DEG C, typical but non-limiting the hydro-thermal reaction time be 10h, 12h, 15h, 16h,
18h, 20h, 22h or for 24 hours.If the temperature of hydro-thermal reaction is too low, the time is too short, and graphene oxide can not then restore, if hydro-thermal is anti-
The temperature answered is excessively high, overlong time, and the graphene restored under high temperature is reunited serious.Therefore the temperature and time of hydro-thermal reaction should control
Within the scope of certain numerical value.
As a kind of optional embodiment of the invention, in step (b), hydro-thermal reaction is in polytetrafluoroethylene (PTFE) reaction vessel
It carries out.In view of safe operation and the tolerable temperature and stress problems of reaction kettle, reducing substances and the first mixed solution shape
At packing ratio of the mixed liquor in polytetrafluoroethylene (PTFE) reaction vessel be 1/2-2/3.
It is dry for freeze-drying in step (b) as a kind of optional embodiment of the invention.Conventional heated drying holds
It easily leads to graphene to reunite seriously, therefore uses freeze-drying, the reunion degree of graphene can be reduced, reach certain dispersion
Uniformity.
To Mn3O4When structure carries out the operation of embedding lithium, the type of selected lithium source is not especially limited.As the present invention
A kind of optional embodiment, in step (b), lithium source includes any one in lithium hydroxide, lithium nitrate, lithium carbonate or lithium acetate
Kind or at least two combination, preferably lithium hydroxide.
As a kind of optional embodiment of the invention, in step (c), the temperature of hydro-thermal reaction is 200-260 DEG C, hydro-thermal
The time of reaction is 18-36h;The temperature of typical but non-limiting hydro-thermal reaction be 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C,
240 DEG C, 250 DEG C or 260 DEG C, typical but non-limiting the hydro-thermal reaction time be 18h, 20h, for 24 hours, 25h, 28h, 30h, 32h,
34h or 36h.If the temperature of hydro-thermal reaction is too low, the time is too short, not can guarantee being effectively embedded into for lithium;If the temperature of hydro-thermal reaction
Excessively high, lattice transformation can occur for overlong time, the LiMn2O4 after embedding lithium, be unfavorable for subsequent electric discharge performance.
As a kind of optional embodiment of the invention, in step (c), solvent includes in ethyl alcohol, ethylene glycol or glycerine
Any one or at least two combination.
Hydrothermal product in step (c) has good dispersion performance in above-mentioned solvent, be conducive to subsequent film at
Type.
As a kind of optional embodiment of the invention, in step (c), hydro-thermal reaction is in polytetrafluoroethylene (PTFE) reaction vessel
It carries out, packing ratio of second mixed solution in polytetrafluoroethylene (PTFE) reaction vessel is 1/2-2/3.
As a kind of optional embodiment of the invention, in step (c), film with a thickness of 2-10 μm.Typical but non-limit
The film of property processed with a thickness of 2 μm, 3 μm, 5 μm, 6 μm, 8 μm or 10 μm.
As a kind of optional embodiment of the invention, lithium ion cell positive is that LiMn2O4 is formed in graphene layer and layer
Between membrane structure, and lithium ion cell positive does not include collector and bonding agent.
I.e. the lithium ion cell positive is using graphene as conductive network, LiMn2O4As active material, wherein LiMn2O4
It is a kind of excellent lithium ion storage and transmission material, has good ionic conductivity, higher capacity can be provided.The lithium
Ion battery is just extremely exempting from the membrane electrode of collector and bonding agent, and the energy density of battery entirety can be improved.
According to the second aspect of the invention, a kind of lithium ion cell positive is additionally provided.The lithium ion cell positive is
The membrane electrode structure for exempting from collector and bonding agent can be improved the energy density of battery entirety, and will not be made due to collector
Its application is influenced with limited.Meanwhile the lithium ion cell positive can effectively inhibit anode during lithium ion deintercalation
Bulk effect, keep electrode integrality, improve the cycle life of battery.
According to the third aspect of the present invention, a kind of lithium ion battery is additionally provided, includes above-mentioned lithium ion cell positive.
In view of advantage possessed by above-mentioned lithium ion cell positive, so that lithium ion battery energy density with higher
And longer cycle life.
According to the fourth aspect of the present invention, a kind of electric device is additionally provided, includes above-mentioned lithium ion battery.In view of upper
Advantage possessed by lithium ion battery is stated, can also be obtained in the electric device of the lithium ion battery using embodiment of the present invention
Identical effect.
In addition to above-mentioned lithium ion battery applications in electric device, can also be applied to electronic device, electric tool, electricity
In motor-car and power storage system.
Electronic device is the electricity for using lithium ion battery to perform various functions (for example, performing music) as the power supply of operation
Sub-device.Electric tool is the electric tool for using lithium ion battery to carry out moving parts (for example, drill bit) as driving power.Electricity
Motor-car is the electric vehicle run by lithium ion battery as driving power, and be can be other than lithium ion battery
It is also equipped with the automobile (including hybrid electric vehicle) of other driving sources.Electric power storage system is to use lithium ion battery as electric power
The electric power storage system of storage source.For example, making electric power be stored in the lithium as electric power storage source in household power stocking system
In ion battery, and the electric power that consumption is stored in lithium ion battery as needed is to be able to use such as domestic electronic appliances
Various devices.
Combined with specific embodiments below and comparative example, the invention will be further described.
Embodiment 1
Present embodiments provide a kind of preparation method of lithium ion cell positive, comprising the following steps:
(a) crystalline flake graphite of 100 mesh of 3g and 18g potassium permanganate are added to 400mL mixed acid (sulfuric acid and phosphoric acid, volume
Than forming mixed liquor for 30min is mixed in 7:1);
Mixed liquor is placed on magnetic stirring apparatus and is stirred and heated to 45 DEG C or so, reacts 12h, after reaction under ice bath slowly
400mL deionized water is added, after reacting balance, is added 20mL hydrogen peroxide, solution turned yellow, the reaction was continued 4h obtains the first mixing
Solution;
(b) reducing substances ethylenediamine is mixed with the first mixed solution, adjusts the pH of the first mixed solution to neutrality, so
After transfer them in polytetrafluoroethylene (PTFE) reactor, seal, in 120 DEG C of progress hydro-thermal reaction 18h;
After the washing of obtained hydrothermal product, freeze-drying, ultrasonic disperse is obtained in the solution mixing containing lithium hydroxide
Second mixed solution;
(c) the second mixed solution is transferred in polytetrafluoroethylene (PTFE) reactor, is sealed, in 220 DEG C of progress hydro-thermal reactions
24h;
Obtained hydrothermal product is washed, is then dispersed in ethyl alcohol, film is made in spraying drying, obtains lithium ion battery
Anode.
Embodiment 2
Present embodiments provide a kind of preparation method of lithium ion cell positive, comprising the following steps:
(a) crystalline flake graphite of 100 mesh of 3g and 18g potassium permanganate are added to 400mL mixed acid (sulfuric acid and phosphoric acid, volume
Than forming mixed liquor for 30min is mixed in 3:1);
Mixed liquor is placed on magnetic stirring apparatus and is stirred and heated to 45 DEG C or so, reacts 12h, after reaction under ice bath slowly
400mL deionized water is added, after reacting balance, is added 20mL hydrogen peroxide, solution turned yellow, the reaction was continued 4h obtains the first mixing
Solution;
(b) reducing substances ethylenediamine is added in the first mixed solution and adjusts the pH of the first mixed solution into
Property, it is then transferred in polytetrafluoroethylene (PTFE) reactor, seals, for 24 hours in 100 DEG C of progress hydro-thermal reactions;
After the washing of obtained hydrothermal product, freeze-drying, ultrasonic disperse is obtained in the solution mixing containing lithium hydroxide
Second mixed solution;
(c) the second mixed solution is transferred in polytetrafluoroethylene (PTFE) reactor, is sealed, in 260 DEG C of progress hydro-thermal reactions
18h;
Obtained hydrothermal product is washed, is then dispersed in ethyl alcohol, film is made in spraying drying, obtains lithium ion battery
Anode.
Embodiment 3
Present embodiments provide a kind of preparation method of lithium ion cell positive, comprising the following steps:
(a) crystalline flake graphite of 200 mesh of 3g and 18g potassium permanganate are added to 400mL mixed acid (sulfuric acid and phosphoric acid, volume
Than forming mixed liquor for 30min is mixed in 7:1);
Mixed liquor is placed on magnetic stirring apparatus and is stirred and heated to 45 DEG C or so, reacts 12h, after reaction under ice bath slowly
400mL deionized water is added, after reacting balance, is added 20mL hydrogen peroxide, solution turned yellow, the reaction was continued 4h obtains the first mixing
Solution;
(b) reducing substances ethylenediamine is added in the first mixed solution and adjusts the pH of the first mixed solution into
Property, it is then transferred in polytetrafluoroethylene (PTFE) reactor, seals, for 24 hours in 100 DEG C of progress hydro-thermal reactions;
After the washing of obtained hydrothermal product, freeze-drying, ultrasonic disperse is obtained in the solution mixing containing lithium hydroxide
Second mixed solution;
(c) the second mixed solution is transferred in polytetrafluoroethylene (PTFE) reactor, is sealed, in 200 DEG C of progress hydro-thermal reactions
36h;
Obtained hydrothermal product is washed, is then dispersed in ethyl alcohol, film is made in spraying drying, obtains lithium ion battery
Anode.
Embodiment 4
A kind of preparation method of lithium ion cell positive is present embodiments provided, reducing substances are hydration in step (b)
Hydrazine, remaining step and technological parameter are same as Example 1.
Embodiment 5
A kind of preparation method of lithium ion cell positive is present embodiments provided, reducing substances are hydration in step (b)
Hydrazine, remaining step and technological parameter are same as Example 1.
Embodiment 6
A kind of preparation method of lithium ion cell positive is present embodiments provided, reducing substances are vulcanization in step (b)
Sodium, remaining step and technological parameter are same as Example 1.
Embodiment 7
Present embodiments provide a kind of preparation method of lithium ion cell positive, in step (b) time of hydro-thermal reaction be
28h, remaining step and technological parameter are same as Example 1.
Embodiment 8
A kind of preparation method of lithium ion cell positive is present embodiments provided, the temperature of hydro-thermal reaction is in step (b)
90 DEG C, remaining step and technological parameter are same as Example 1.
Embodiment 9
A kind of preparation method of lithium ion cell positive is present embodiments provided, the temperature of hydro-thermal reaction is in step (c)
280 DEG C, remaining step and technological parameter are same as Example 1.
Embodiment 10
A kind of preparation method of lithium ion cell positive is present embodiments provided, the temperature of hydro-thermal reaction is in step (c)
180 DEG C, remaining step and technological parameter are same as Example 1.
Embodiment 11
Present embodiments provide a kind of preparation method of lithium ion cell positive, in step (c) time of hydro-thermal reaction be
40h, remaining step and technological parameter are same as Example 1.
Embodiment 12
Present embodiments provide a kind of preparation method of lithium ion cell positive, comprising the following steps:
(a) expanded graphite of 200 mesh of 4g and 20g potassium permanganate are added to 500mL mixed acid (sulfuric acid and phosphoric acid, volume
Than forming mixed liquor for 30min is mixed in 4:1);
Mixed liquor is placed on magnetic stirring apparatus and is stirred and heated to 40 DEG C or so, reacts 15h, after reaction under ice bath slowly
400mL deionized water is added, after reacting balance, is added 20mL hydrogen peroxide, solution turned yellow, the reaction was continued 4h obtains the first mixing
Solution;
(b) reducing substances ethylenediamine is added in the first mixed solution and adjusts the pH of the first mixed solution into
Property, it is then transferred in polytetrafluoroethylene (PTFE) reactor, seals, in 140 DEG C of progress hydro-thermal reaction 10h;
After the washing of obtained hydrothermal product, freeze-drying, ultrasonic disperse is obtained in the solution mixing containing lithium hydroxide
Second mixed solution;
(c) the second mixed solution is transferred in polytetrafluoroethylene (PTFE) reactor, is sealed, in 220 DEG C of progress hydro-thermal reactions
20h;
Obtained hydrothermal product is washed, is then dispersed in ethyl alcohol, film is made in spraying drying, obtains lithium ion battery
Anode.
Comparative example 1
This comparative example provides a kind of preparation method of lithium ion cell positive, comprising the following steps:
(a) by graphene oxide and 18g potassium permanganate according to the ratio ultrasonic disperse that mass ratio is 1:36 in 400mL go from
In sub- water, the first mixed solution is obtained;
Step (b) and (c) are same as Example 1.
Comparative example 2
This comparative example provides a kind of preparation method of lithium ion cell positive, comprising the following steps:
It, will by graphene, mangano-manganic oxide according to the ratio ultrasonic disperse that mass ratio is 1:52 in manganous hydroxide solution
Obtained mixed solution is transferred in polytetrafluoroethylene (PTFE) reactor, sealing, for 24 hours in 220 DEG C of progress hydro-thermal reactions;Wherein, graphite
The dosage of alkene is identical as the dosage of graphene in embodiment (1) step (b), the dosage and embodiment (1) step of mangano-manganic oxide
(b) dosage of mangano-manganic oxide is identical in;
Obtained hydrothermal product is washed, is then dispersed in ethyl alcohol, film is made in spraying drying, obtains lithium ion battery
Anode.
For the effect for verifying embodiment and comparative example, ad hoc following experimental example.
Experimental example 1
The lithium ion being prepared for the preparation method further verified using lithium ion cell positive provided by the invention
The shape appearance figure of anode detects the pattern of the lithium ion cell positive of offer herein only by taking embodiment 1 as an example, tool
Body is as shown in Figure 1.
The lithium ion cell positive that the embodiment of the present invention 1 provides it can be seen from Fig. 1 has apparent graphene fold
Structure.
Experimental example 2
For the performance for verifying each obtained lithium ion cell positive of embodiment and comparative example, just as full battery
Pole is assembled into button cell and is tested according to anode-electrolyte-diaphragm-electrolyte-cathode sequence.Detection at room temperature with
When the 5C constant-current discharge of lithium ion cell positive, the cyclical stability of lithium ion battery, concrete outcome are shown in Table 1 after 200 circle of circulation
And Fig. 2.It should be noted that Fig. 2 is the cycle performance figure of the corresponding lithium ion battery of embodiment 1.
The chemical property of the corresponding lithium ion battery of each embodiment and comparative example of table 1
Serial number | Specific capacity (mAh/g) | Energy density |
Embodiment 1 | 138 | 187 |
Embodiment 2 | 136 | 186 |
Embodiment 3 | 135 | 186 |
Embodiment 4 | 133 | 184 |
Embodiment 5 | 133 | 184 |
Embodiment 6 | 120 | 175 |
Embodiment 7 | 118 | 174 |
Embodiment 8 | 121 | 176 |
Embodiment 9 | 114 | 173 |
Embodiment 10 | 122 | 177 |
Embodiment 11 | 120 | 175 |
Embodiment 12 | 119 | 175 |
Comparative example 1 | 74 | 104 |
Comparative example 2 | 59 | 89 |
Specifically, it can be seen from the data in Table 1 that the performance of lithium ion battery corresponding to various embodiments of the present invention wants whole
Performance of the body better than lithium ion battery corresponding to each comparative example.It can be seen that lithium ion cell positive provided by the invention can
Effectively promote the energy density and cyclical stability of lithium ion battery.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations;To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement;And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of lithium ion cell positive, which is characterized in that include the following steps;
(a) graphite, potassium permanganate and mixed acid are mixed, water and hydrogen peroxide is added in reaction after reaction, the reaction was continued, obtains the
One mixed solution;
(b) reducing substances are mixed with the first mixed solution, carry out hydro-thermal reaction, by obtained hydrothermal product it is dry after with contain
There is the solution of lithium source to mix, obtains the second mixed solution;
(c) the second mixed solution is subjected to hydro-thermal reaction, disperses obtained hydrothermal product in solvent, film is made, obtains
Lithium ion cell positive.
2. the preparation method of lithium ion cell positive according to claim 1, which is characterized in that in step (a), the stone
Ink includes the combination of any one or at least two in crystalline flake graphite, expanded graphite, graphite oxide or thermal cracking graphite, preferably
For crystalline flake graphite;
And/or in step (a), the granularity of the graphite is 50-200 mesh;
And/or in step (a), the mixed acid includes sulfuric acid and phosphoric acid, and the volume ratio of sulfuric acid and phosphoric acid is (3-7): 1;
And/or in step (a), the mass ratio of the graphite, potassium permanganate and mixed acid is (0.16-0.5): (1-3): (40-
72);
And/or in step (a), the temperature of the reaction is 40-50 DEG C, and the time of the reaction is 10-15h.
3. the preparation method of lithium ion cell positive according to claim 1, which is characterized in that described to go back in step (b)
Immunogenic substance is to contain NH4+Reproducibility alkaline matter, preferably include ethylenediamine and/or hydrazine hydrate;
And/or in step (b), the dosage of the reducing substances of addition is to reach the pH value of first mixed solution
It is neutral;
And/or in step (b), the temperature of the hydro-thermal reaction is 100-140 DEG C, and the time of the hydro-thermal reaction is 10-24h;
And/or in step (b), the drying is freeze-drying;
And/or in step (b), the lithium source include in lithium hydroxide, lithium nitrate, lithium carbonate or lithium acetate any one or
The combination of person at least two.
4. the preparation method of lithium ion cell positive according to claim 1, which is characterized in that in step (c), the water
The temperature of thermal response is 200-260 DEG C, and the time of the hydro-thermal reaction is 18-36h;
And/or in step (c), the solvent includes any one or at least two in ethyl alcohol, ethylene glycol or glycerine
Combination.
5. the preparation method of lithium ion cell positive according to claim 1, which is characterized in that in step (b), the water
Thermal response carries out in polytetrafluoroethylene (PTFE) reaction vessel, and the mixed liquor that the reducing substances and the first mixed solution are formed is poly-
Packing ratio in tetrafluoroethene reaction vessel is 1/2-2/3;
And/or in step (c), the hydro-thermal reaction carries out in polytetrafluoroethylene (PTFE) reaction vessel, and second mixed solution exists
Packing ratio in polytetrafluoroethylene (PTFE) reaction vessel is 1/2-2/3.
6. the preparation method of lithium ion cell positive described in -5 any one according to claim 1, which is characterized in that step
(c) in, the film with a thickness of 2-10 μm.
7. the preparation method of lithium ion cell positive described in -5 any one according to claim 1, which is characterized in that the lithium
Just extremely LiMn2O4 is formed in the membrane structure of graphene between layers to ion battery, and the lithium ion cell positive does not wrap
Include collector and bonding agent.
8. a kind of lithium ion cell positive, which is characterized in that just using lithium ion battery described in claim 1-7 any one
The preparation method of pole is prepared;
The lithium ion cell positive is that LiMn2O4 is formed in the membrane structure of graphene between layers, and the lithium-ion electric
Pond anode does not include collector and bonding agent.
9. a kind of lithium ion battery, which is characterized in that include lithium ion cell positive according to any one of claims 8.
10. a kind of electric device, which is characterized in that include lithium ion battery as claimed in claim 9.
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