CN108598367A - A kind of high voltage negative plate and preparation method thereof, a kind of high-voltage lithium - Google Patents
A kind of high voltage negative plate and preparation method thereof, a kind of high-voltage lithium Download PDFInfo
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- CN108598367A CN108598367A CN201810385887.9A CN201810385887A CN108598367A CN 108598367 A CN108598367 A CN 108598367A CN 201810385887 A CN201810385887 A CN 201810385887A CN 108598367 A CN108598367 A CN 108598367A
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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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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The present invention relates to technical field of lithium batteries, and in particular to a kind of high voltage negative plate and preparation method thereof, a kind of high-voltage lithium, the high voltage negative plate includes negative current collector and the negative electrode slurry layer coated on the negative current collector surface, it is characterised in that：The negative electrode slurry layer carries out carbonization treatment by the first binder of the cellulose of 50wt% 70wt%, the graphene of 29wt% 47wt% and 1wt% 3wt% and is made.The present invention uses active material one of of the graphene as lithium battery cathode plate, the storage lithium ability of battery can be greatlyd improve, and then promote energy density, and improve the conductive network structure of negative electrode slurry layer by carbonization, it is more advantageous to the insertion deintercalation of lithium, the dosage for reducing graphene simultaneously, reduces cost.
Description
Technical field
The present invention relates to technical field of lithium batteries, and in particular to a kind of high voltage negative plate and preparation method thereof, Yi Zhonggao
Voltage lithium cells.
Background technology
With the fast development of electronic equipment and becoming increasingly conspicuous for energy and environment problem, people propose electrochmical power source
Higher requirement.Lithium ion battery with its high voltage, it is bigger than energy, have extended cycle life, it is pollution-free the advantages that it is fast on the market
Speed emerges, and becomes a kind of Novel clean, the high energy energy.It is various portable electronic devices, wireless especially into 21st century
The fast development and extensive use of mobile communication equipment, electric vehicle, for more height ratio capacity, service life cycle it is long, it is low at
The demand of this lithium ion battery seems more urgent.
Improve lithium ion battery high-energy-density index key be high-energy-density positive active material exploitation and, and it is big
Most researchers have put into main attention the exploitation of the positive active material of high-energy-density, and ignore setting for negative electrode
Meter.
The cathode of lithium ion battery is by carbon element or non-carbon material, adhesive and additive mixing system
Copper foil both sides are uniformly applied at paste adhesive, through drying, are rolled.Lithium ion battery success it is made, it is crucial
It is to prepare the negative material of reversibly de-/embedding lithium ion.Currently, being actually used in the negative material of lithium ion battery
Typically carbon materials, such as graphite, soft carbon (such as coke), hard carbon.The negative material explored have nitride, PAS,
Tin-based oxide, tin alloy, nanometer anode material, and some other intermetallic compounds etc..Therefore, by improving cathode
Active material can improve lithium ion battery specific capacity and service life cycle, and can also be lived by developing novel cathode
Property substance reduce lithium battery cost.
Invention content
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of height ratio capacity,
Long, the inexpensive high voltage negative plate of service life cycle, another object of the present invention is to provide the high voltage negative plates
Preparation method is carbonized afterwards by first coating, and can be made the layer structure for improving graphene in cellulose carbonisation, is more suitable for lithium
Insertion-deintercalation there is Fabrication of High Specific Capacitance another object of the present invention is to provide the lithium battery made of the high voltage negative plate
The advantages that amount, service life cycle are long, inexpensive.
The purpose of the invention is achieved by the following technical solution：
A kind of high voltage negative plate, including negative current collector and the negative electrode slurry coated on the negative current collector surface
Layer, the negative electrode slurry layer is by the cellulose of 50wt%-70wt%, the graphene of 29wt%-47wt% and 1wt%-3wt%
First binder carries out carbonization treatment and is made.
Wherein, the length of the cellulose is 20-60 μm, and the average grain diameter of a diameter of 200-300nm, the graphene are
30-80nm, BET surface area 300-700m2/g.By the parameters of control fiber element and graphene, can be effectively improved
The dispersibility and electric conductivity of the two, and the more firm conductive network structure of more enough formation after cellulose carbonization, improve compacting
Density, to improve the cycle performance of negative plate of the present invention
Wherein, the first binder is the mixture of one or both of Kynoar, polytetrafluoroethylene (PTFE).
The present invention also provides the preparation methods of this kind of high voltage negative plate：According to the ratio by cellulose, graphene and first
After binder is mixed in a certain amount of organic solvent, negative electrode slurry is formed, the negative electrode slurry is coated on described
It on negative current collector, is then dried, is placed in progress high temperature cabonization 0.5-2h under 1000-1400 DEG C of atmosphere of inert gases,
Obtain the high voltage negative plate.The structure of conductive network can be effectively controlled by controlling carbonization time and carburizing temperature
It generates, to improve the energy density of negative plate.
The present invention also provides a kind of high-voltage lithiums, including positive plate, electrolyte, diaphragm and high voltage as described above
Negative plate.
Wherein, the positive plate includes the anode sizing agent layer of plus plate current-collecting body and coating and plus plate current-collecting body surface, described
Anode sizing agent layer is by the of the positive active material of 87wt%-95wt%, the conductive agent of 4wt%-10wt% and 1wt%-3wt%
Two binders form, and the positive active material is LiNixCoyMnzO2, wherein 0.26≤x≤0.33,0.44≤y≤0.61,
0.06≤z≤0.3, and x+y+z=1.The application is with Ni (NO3)2·6H2O、Co(NO3)2·6H2O、Mn(NO3)2、LiOH·H2O
For raw material, novel cobalt-nickel-manganese oxide compound is prepared using coprecipitation, there is spy at low cost, point is high, stability is strong
Point can effectively improve the specific capacity of the present invention.
Wherein, the conductive agent by carbon nanotube and electrically conductive graphite by weight 2-3:1 ratio composition.
Wherein, second binder is Kynoar.
Wherein, the plus plate current-collecting body is made by alloy foil by corrosion treatment, and the ingredient of the alloy foil is as follows：
Remaining is aluminium and inevitable impurity.
There is the alloy foil of the present invention preferable mechanical property, tensile strength to be up to 200-220MPa, simultaneously because tool
The Fe elements for having high level can generate porous property when forming Alloy Foil, to be conducive to positive electrode active material of the present invention
The attachment of matter and conductive agent, it is not easy to generate picking phenomenon, good cycle；And porous alloy foil also has larger ratio table
Area, electrical efficiency higher, to improve the specific discharge capacity of the present invention.
Further, the preparation method of the plus plate current-collecting body includes the following steps：A, the preparation of alloy foil：It is closed by aluminium
The composition proportion of goldleaf weighs metal simple-substance or intermediate alloy and carries out melting, Homogenization Treatments, cold rolling and two-stage time effect successively, system
Obtain the alloy foil；B, corrosion treatment：Direct current energization, current density 0.1-0.2A/cm are carried out to alloy foil2, and will
Alloy foil, which is placed in the HCl solution of a concentration of 0.05-0.2mol/L, to be corroded, then etching time 7-10min is spent
Ionized water and washes of absolute alcohol are to get to plus plate current-collecting body.By further corrosion treatment, the more of foil can be enabled aluminum alloy to
Porous is more notable, has higher porosity and more suitable micropore size, is conducive to improve electrical efficiency and anode is starched
The adhesive force of the bed of material.
Further, the temperature of the melting is 720-740 DEG C, and the temperature of the Homogenization Treatments is 600-660 DEG C,
The time for homogenizing processing is 4-8h, and the two-stage time effect is that 10-14h is kept the temperature at 120-140 DEG C, is kept the temperature later at 180-200 DEG C
30-50min.By controlling the preparation parameter of alloy foil, can enable aluminum alloy to foil has suitable mechanical property and electric conductivity
Energy.
Wherein, the micropore size on the plus plate current-collecting body surface is 20-60 μm, and the porosity of the plus plate current-collecting body is
The thickness of 18-22%, the plus plate current-collecting body are 6-20 μm.
The beneficial effects of the present invention are：1, the present invention using graphene as lithium battery cathode plate active material it
One, the storage lithium ability of battery can be greatlyd improve, and then promote energy density；2, the present invention using cellulose to graphene into
Row blending and modifying is then improved the conductive network structure of negative electrode slurry layer by carbonization, is more advantageous to insertion-deintercalation of lithium, together
When reduce graphene dosage, reduce cost；3, cellulose of the invention is forming negative electrode slurry and is being coated in negative current collector
When upper, cohesive effect can be played, so as to reduce the use of binder, then so that cellulose is converted by high temperature cabonization
For the carbon fiber with excellent electrical conductivity, makes negative electrode slurry layer that there is good conductive structure, be not easy shedding；4, the present invention is utilized
Lithium battery made of high voltage negative plate has many advantages, such as that height ratio capacity, service life cycle are long, inexpensive.
Description of the drawings
Fig. 1 is the circulating battery schematic diagram of embodiment 1；
Specific implementation mode
For the ease of the understanding of those skilled in the art, the present invention is made with reference to embodiment and attached drawing 1 further
Illustrate, the content that embodiment refers to not is limitation of the invention.
Embodiment 1
A kind of high voltage negative plate, including negative current collector and the negative electrode slurry coated on the negative current collector surface
Layer, the negative electrode slurry layer carry out carbonization by the first binder of the cellulose of 60wt%, the graphene of 38wt% and 2wt%
Reason is made.
Wherein, the length of the cellulose is 40 μm, a diameter of 250nm, and the average grain diameter of the graphene is 55nm,
BET surface area is 500m2/g。
Wherein, the first binder is Kynoar.
The present invention also provides the preparation methods of this kind of high voltage negative plate：According to the ratio by cellulose, graphene and first
After binder is mixed in the N-Methyl pyrrolidone of their 10 times of amounts, negative electrode slurry is formed, by the negative electrode slurry
It coated on the negative current collector, is then dried, is placed under 1200 DEG C of atmosphere of inert gases and carries out high temperature cabonization
1.2h is to get to the high voltage negative plate.
The present invention also provides a kind of high-voltage lithiums, including positive plate, electrolyte, diaphragm and high voltage as described above
Negative plate.
Wherein, the positive plate includes the anode sizing agent layer of plus plate current-collecting body and coating and plus plate current-collecting body surface, described
Anode sizing agent layer is made of the second binder of the positive active material of 91wt%, the conductive agent of 7wt% and 2wt%, it is described just
Pole active material is LiNixCoyMnzO2, wherein wherein x=0.3, y=0.5, z=0.2.
Wherein, the conductive agent is by carbon nanotube and electrically conductive graphite by weight 2.5:1 ratio composition.
Wherein, second binder is Kynoar.
Wherein, the plus plate current-collecting body is made by alloy foil by corrosion treatment, and the ingredient of the alloy foil is as follows：
Remaining is aluminium and inevitable impurity.
Further, the preparation method of the plus plate current-collecting body includes the following steps：A, the preparation of alloy foil：It is closed by aluminium
The composition proportion of goldleaf weighs metal simple-substance or intermediate alloy and carries out melting, Homogenization Treatments, cold rolling and two-stage time effect successively, system
Obtain the alloy foil；B, corrosion treatment：Direct current energization, current density 0.15A/cm are carried out to alloy foil2, and aluminium is closed
Goldleaf, which is placed in the HCl solution of a concentration of 0.12mol/L, to be corroded, etching time 8.5min, then use deionized water and
Washes of absolute alcohol is to get to plus plate current-collecting body.
Further, the temperature of the melting is 730 DEG C, and the temperature of the Homogenization Treatments is 630 DEG C, Homogenization Treatments
Time be 6h, the two-stage time effect be at 130 DEG C keep the temperature 12h, later at 190 DEG C keep the temperature 40min.
Wherein, the micropore size on the plus plate current-collecting body surface is 40 μm, and the porosity of the plus plate current-collecting body is 20%,
The thickness of the plus plate current-collecting body is 13 μm.
Embodiment 2
A kind of high voltage negative plate, including negative current collector and the negative electrode slurry coated on the negative current collector surface
Layer, the negative electrode slurry layer carry out carbonization by the first binder of the cellulose of 50wt%, the graphene of 47wt% and 3wt%
Reason is made.
Wherein, the length of the cellulose is 20 μm, a diameter of 200nm, and the average grain diameter of the graphene is 30nm,
BET surface area is 700m2/g。
Wherein, the first binder is Kynoar.
The present invention also provides the preparation methods of this kind of high voltage negative plate：According to the ratio by cellulose, graphene and first
After binder is mixed in the N-Methyl pyrrolidone of their 10 times of amounts, negative electrode slurry is formed, by the negative electrode slurry
It coated on the negative current collector, is then dried, is placed under 1000 DEG C of atmosphere of inert gases and carries out high temperature cabonization
2h is to get to the high voltage negative plate.
The present invention also provides a kind of high-voltage lithiums, including positive plate, electrolyte, diaphragm and high voltage as described above
Negative plate.
Wherein, the positive plate includes the anode sizing agent layer of plus plate current-collecting body and coating and plus plate current-collecting body surface, described
Anode sizing agent layer is made of the second binder of the positive active material of 87wt%, the conductive agent of 10wt% and 3wt%, it is described just
Pole active material is LiNixCoyMnzO2, wherein x=0.26, y=0.44, z=0.3.
Wherein, the conductive agent is by carbon nanotube and electrically conductive graphite by weight 2:1 ratio composition.
Wherein, second binder is Kynoar.
Wherein, the plus plate current-collecting body is made by alloy foil by corrosion treatment, and the ingredient of the alloy foil is as follows：
Remaining is aluminium and inevitable impurity.
Further, the preparation method of the plus plate current-collecting body includes the following steps：A, the preparation of alloy foil：It is closed by aluminium
The composition proportion of goldleaf weighs metal simple-substance or intermediate alloy and carries out melting, Homogenization Treatments, cold rolling and two-stage time effect successively, system
Obtain the alloy foil；B, corrosion treatment：Direct current energization, current density 0.1A/cm are carried out to alloy foil2, and aluminium is closed
Goldleaf, which is placed in the HCl solution of a concentration of 0.05mol/L, to be corroded, etching time 7min, then uses deionized water and nothing
Water-ethanol cleaning is to get to plus plate current-collecting body.
Further, the temperature of the melting is 720 DEG C, and the temperature of the Homogenization Treatments is 600 DEG C, Homogenization Treatments
Time be 4h, the two-stage time effect be at 120 DEG C keep the temperature 10h, later at 180 DEG C keep the temperature 30min.
Wherein, the micropore size on the plus plate current-collecting body surface is 20 μm, and the porosity of the plus plate current-collecting body is 18%,
The thickness of the plus plate current-collecting body is 6 μm.
Embodiment 3
A kind of high voltage negative plate, including negative current collector and the negative electrode slurry coated on the negative current collector surface
Layer, the negative electrode slurry layer carry out carbonization by the first binder of the cellulose of 70wt%, the graphene of 29wt% and 1wt%
Reason is made.
Wherein, the length of the cellulose is 60 μm, a diameter of 300nm, and the average grain diameter of the graphene is 80nm,
BET surface area is 300m2/g。
Wherein, the first binder is Kynoar.
The present invention also provides the preparation methods of this kind of high voltage negative plate：According to the ratio by cellulose, graphene and first
After binder is mixed in the N-Methyl pyrrolidone of their 10 times of amounts, negative electrode slurry is formed, by the negative electrode slurry
It coated on the negative current collector, is then dried, is placed under 1400 DEG C of atmosphere of inert gases and carries out high temperature cabonization
0.5h is to get to the high voltage negative plate.
The present invention also provides a kind of high-voltage lithiums, including positive plate, electrolyte, diaphragm and high voltage as described above
Negative plate.
Wherein, the positive plate includes the anode sizing agent layer of plus plate current-collecting body and coating and plus plate current-collecting body surface, described
Anode sizing agent layer is made of the second binder of the positive active material of 95wt%, the conductive agent of 4wt% and 1wt%, it is described just
Pole active material is LiNixCoyMnzO2, wherein x=0.33, y=0.61, z=0.6.
Wherein, the conductive agent is by carbon nanotube and electrically conductive graphite by weight 3:1 ratio composition.
Wherein, second binder is Kynoar.
Wherein, the plus plate current-collecting body is made by alloy foil by corrosion treatment, and the ingredient of the alloy foil is as follows：
Remaining is aluminium and inevitable impurity.
Further, the preparation method of the plus plate current-collecting body includes the following steps：A, the preparation of alloy foil：It is closed by aluminium
The composition proportion of goldleaf weighs metal simple-substance or intermediate alloy and carries out melting, Homogenization Treatments, cold rolling and two-stage time effect successively, system
Obtain the alloy foil；B, corrosion treatment：Direct current energization, current density 0.2A/cm are carried out to alloy foil2, and aluminium is closed
Goldleaf, which is placed in the HCl solution of a concentration of 0.2mol/L, to be corroded, etching time 10min, then uses deionized water and nothing
Water-ethanol cleaning is to get to plus plate current-collecting body.
Further, the temperature of the melting is 740 DEG C, and the temperature of the Homogenization Treatments is 660 DEG C, Homogenization Treatments
Time be 8h, the two-stage time effect be at 140 DEG C keep the temperature 14h, later at 200 DEG C keep the temperature 50min.
Wherein, the micropore size on the plus plate current-collecting body surface is 60 μm, and the porosity of the plus plate current-collecting body is 22%,
The thickness of the plus plate current-collecting body is 20 μm.
Embodiment 4
A kind of high voltage negative plate, including negative current collector and the negative electrode slurry coated on the negative current collector surface
Layer, the negative electrode slurry layer carry out carbon by the first binder of the cellulose of 55wt%, the graphene of 43.5wt% and 1.5wt%
Change processing is made.
Wherein, the length of the cellulose is 30 μm, a diameter of 220nm, and the average grain diameter of the graphene is 40nm,
BET surface area is 600m2/g。
Wherein, the first binder is by Kynoar and polytetrafluoroethylene (PTFE) by weight 1:1 composition.
The present invention also provides the preparation methods of this kind of high voltage negative plate：According to the ratio by cellulose, graphene and first
After binder is mixed in the N-Methyl pyrrolidone of their 10 times of amounts, negative electrode slurry is formed, by the negative electrode slurry
It coated on the negative current collector, is then dried, is placed under 1100 DEG C of atmosphere of inert gases and carries out high temperature cabonization
1.5h is to get to the high voltage negative plate.
The present invention also provides a kind of high-voltage lithiums, including positive plate, electrolyte, diaphragm and high voltage as described above
Negative plate.
Wherein, the positive plate includes the anode sizing agent layer of plus plate current-collecting body and coating and plus plate current-collecting body surface, described
Anode sizing agent layer is made of the second binder of the positive active material of 90wt%, the conductive agent of 7wt% and 3wt%, it is described just
Pole active material is LiNixCoyMnzO2, wherein x=0.28, y=0.55, z=0.17.
Wherein, the conductive agent is by carbon nanotube and electrically conductive graphite by weight 2.2:1 ratio composition.
Wherein, second binder is Kynoar.
Wherein, the plus plate current-collecting body is made by alloy foil by corrosion treatment, and the ingredient of the alloy foil is as follows：
Remaining is aluminium and inevitable impurity.
Further, the preparation method of the plus plate current-collecting body includes the following steps：A, the preparation of alloy foil：It is closed by aluminium
The composition proportion of goldleaf weighs metal simple-substance or intermediate alloy and carries out melting, Homogenization Treatments, cold rolling and two-stage time effect successively, system
Obtain the alloy foil；B, corrosion treatment：Direct current energization, current density 0.13A/cm are carried out to alloy foil2, and aluminium is closed
Goldleaf, which is placed in the HCl solution of a concentration of 0.1mol/L, to be corroded, etching time 8min, then uses deionized water and anhydrous
Ethyl alcohol cleaning is to get to plus plate current-collecting body.
Further, the temperature of the melting is 725 DEG C, and the temperature of the Homogenization Treatments is 620 DEG C, Homogenization Treatments
Time be 5h, the two-stage time effect be at 125 DEG C keep the temperature 11h, later at 185 DEG C keep the temperature 35min.
Wherein, the micropore size on the plus plate current-collecting body surface is 30 μm, and the porosity of the plus plate current-collecting body is 19%,
The thickness of the plus plate current-collecting body is 10 μm.
Embodiment 5
A kind of high voltage negative plate, including negative current collector and the negative electrode slurry coated on the negative current collector surface
Layer, the negative electrode slurry layer carry out carbon by the first binder of the cellulose of 65wt%, the graphene of 32.5wt% and 2.5wt%
Change processing is made.
Wherein, the length of the cellulose is 50 μm, a diameter of 280nm, and the average grain diameter of the graphene is 70nm,
BET surface area is 400m2/g。
Wherein, the first binder is polytetrafluoroethylene (PTFE).
The present invention also provides the preparation methods of this kind of high voltage negative plate：According to the ratio by cellulose, graphene and first
After binder is mixed in the N-Methyl pyrrolidone of their 10 times of amounts, negative electrode slurry is formed, by the negative electrode slurry
It coated on the negative current collector, is then dried, is placed under 1300 DEG C of atmosphere of inert gases and carries out high temperature cabonization
1h is to get to the high voltage negative plate.
The present invention also provides a kind of high-voltage lithiums, including positive plate, electrolyte, diaphragm and high voltage as described above
Negative plate.
Wherein, the positive plate includes the anode sizing agent layer of plus plate current-collecting body and coating and plus plate current-collecting body surface, described
Anode sizing agent layer is made of the second binder of the positive active material of 93wt%, the conductive agent of 4.5wt% and 2.5wt%, institute
It is LiNi to state positive active materialxCoyMnzO2, wherein x=0.32, y=0.45, z=0.23.
Wherein, the conductive agent is by carbon nanotube and electrically conductive graphite by weight 2.7:1 ratio composition.
Wherein, second binder is Kynoar.
Wherein, the plus plate current-collecting body is made by alloy foil by corrosion treatment, and the ingredient of the alloy foil is as follows：
Remaining is aluminium and inevitable impurity.
Further, the preparation method of the plus plate current-collecting body includes the following steps：A, the preparation of alloy foil：It is closed by aluminium
The composition proportion of goldleaf weighs metal simple-substance or intermediate alloy and carries out melting, Homogenization Treatments, cold rolling and two-stage time effect successively, system
Obtain the alloy foil；B, corrosion treatment：Direct current energization, current density 0.18A/cm are carried out to alloy foil2, and aluminium is closed
Goldleaf, which is placed in the HCl solution of a concentration of 0.15mol/L, to be corroded, etching time 9min, then uses deionized water and nothing
Water-ethanol cleaning is to get to plus plate current-collecting body.
Further, the temperature of the melting is 735 DEG C, and the temperature of the Homogenization Treatments is 650 DEG C, Homogenization Treatments
Time be 7h, the two-stage time effect be at 135 DEG C keep the temperature 13h, later at 195 DEG C keep the temperature 45min.
Wherein, the micropore size on the plus plate current-collecting body surface is 50 μm, and the porosity of the plus plate current-collecting body is 21%,
The thickness of the plus plate current-collecting body is 15 μm.
Comparative example 1
This comparative example lithium battery and embodiment 1 difference lies in：The negative electrode slurry layer by 98wt% electrically conductive graphite and
The binder of 2wt% forms.
6 performance test of embodiment
By embodiment 1-5 and the lithium battery of comparative example 1 with 0.1C constant-current charges to 4.5V, in 4.5V constant-voltage charges to electric current
For 0.05C, after standing 5min, with the electric current constant-current discharge of 0.1C to 3.0V, the specific capacity discharged for the first time is recorded.
In 3.0V-4.5V voltage ranges, charge and discharge cycles are carried out to battery, the charge and discharge under 1C multiplying powers record battery
Through 400 circulation volume conservation rates, and record the cycle life curve of embodiment 1, such as Fig. 1.
The data of record such as following table：
| First week specific discharge capacity (mAh/g) | Through 400 circulation volume conservation rates (%) | |
| Embodiment 1 | 192.1 | 85.8 |
| Embodiment 2 | 189.6 | 82.7 |
| Embodiment 3 | 189.7 | 82.3 |
| Embodiment 4 | 186.5 | 78.5 |
| Embodiment 5 | 186.6 | 78.9 |
| Comparative example 1 | 178.4 | 73.6 |
By upper table and Fig. 1 it is found that the lithium battery of the present invention has excellent specific capacity and cycle performance, from 1 He of embodiment
The comparison of comparative example 1 it is found that the present invention is improved by the composition to negative electrode slurry layer, substantially improve specific discharge capacity and
Cycle performance, and the characteristic (3.0V-4.5V) with high voltage, and due to using lower-cost cellulose as cathode
Active material, it may have lower cost, industrial production value are high.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other manner,
Any obvious replacement is not departed under the premise of present inventive concept within protection scope of the present invention.
Claims (10)
1. a kind of high voltage negative plate, including negative current collector and the negative electrode slurry layer coated on the negative current collector surface,
It is characterized in that：The negative electrode slurry layer by the cellulose of 50wt%-70wt%, the graphene of 29wt%-47wt% and
The first binder of 1wt%-3wt% carries out carbonization treatment and is made.
2. a kind of high voltage negative plate according to claim 1, it is characterised in that：The length of the cellulose is 20-60 μ
The average grain diameter of m, a diameter of 200-300nm, the graphene are 30-80nm, and BET surface area is 300-700 ㎡/g.
3. a kind of high voltage negative plate according to claim 1, it is characterised in that：The first binder is polyvinylidene fluoride
The mixture of one or both of alkene, polytetrafluoroethylene (PTFE).
4. a kind of preparation method of high voltage negative plate described in claim 1-3 any one, it is characterised in that：According to the ratio will
After cellulose, graphene and first binder are mixed in a certain amount of organic solvent, negative electrode slurry is formed, it will be described negative
Pole slurry be coated on the negative current collector on, then dried, be placed under 1000-1400 DEG C of atmosphere of inert gases into
Row high temperature cabonization 0.5-2h is to get to the high voltage negative plate.
5. a kind of high-voltage lithium, including positive plate, electrolyte, diaphragm, it is characterised in that：Further include that claim 1-3 appoints
High voltage negative plate described in meaning one.
6. a kind of high-voltage lithium according to claim 5, it is characterised in that：The positive plate includes plus plate current-collecting body
With coating and the anode sizing agent layer on plus plate current-collecting body surface, the anode sizing agent layer by 87wt%-95wt% positive electrode active material
Second binder of matter, the conductive agent of 4wt%-10wt% and 1wt%-3wt% forms, and the positive active material is
LiNixCoyMnzO2, wherein 0.26≤x≤0.33,0.44≤y≤0.61,0.06≤z≤0.3, and x+y+z=1.
7. a kind of high-voltage lithium according to claim 6, it is characterised in that：The conductive agent is by carbon nanotube and leads
Electro-graphitic is by weight 2-3:1 ratio composition.
8. a kind of high-voltage lithium according to claim 6, it is characterised in that：The plus plate current-collecting body is by alloy foil
It is made by corrosion treatment, the ingredient of the alloy foil is as follows：
Remaining is aluminium and inevitable impurity.
9. a kind of high-voltage lithium according to claim 8, it is characterised in that：The preparation method of the plus plate current-collecting body
Include the following steps：A, the preparation of alloy foil：Metal simple-substance or intermediate alloy are weighed by the composition proportion of alloy foil successively
Melting, Homogenization Treatments, cold rolling and two-stage time effect are carried out, the alloy foil is made；B, corrosion treatment：Alloy foil is carried out
Direct current is powered, current density 0.1-0.2A/cm2, and alloy foil is placed in the HCl solution of a concentration of 0.05-0.2mol/L
In corroded, then etching time 7-10min uses deionized water and washes of absolute alcohol to get to plus plate current-collecting body.
10. a kind of high-voltage lithium according to claim 9, it is characterised in that：The temperature of the melting is 720-740
DEG C, the temperature of the Homogenization Treatments is 600-660 DEG C, and time of Homogenization Treatments is 4-8h, the two-stage time effect be
120-140 DEG C of heat preservation 10-14h, keeps the temperature 30-50min at 180-200 DEG C later.
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