CN1416189A - Lithium secondary battery by use of composite material covered with nano surface as active material of positive polar - Google Patents

Lithium secondary battery by use of composite material covered with nano surface as active material of positive polar Download PDF

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CN1416189A
CN1416189A CN01134448A CN01134448A CN1416189A CN 1416189 A CN1416189 A CN 1416189A CN 01134448 A CN01134448 A CN 01134448A CN 01134448 A CN01134448 A CN 01134448A CN 1416189 A CN1416189 A CN 1416189A
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licoo
lithium secondary
battery
secondary battery
composite material
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CN1208866C (en
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王兆翔
刘立君
陈立泉
黄学杰
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Institute of Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The lithium secondary battery consists of the positive electrode, the negative electrode, the electrolyte solution or the polymer dielectric or the membrane of the solid electrolyte, the affluxion body, the battery case and the lead wire. The active material of the positive electrode is nano modified composite material covered in the surface. The negative electrode is the material capable of storing lithium. The said composite material covered is one or more substance among semimetals, oxides or salts with the grain diameter being as 0.1-200 nm and the thickness 0.5-200 nm. The invented battery features high reversible capacitnace, good periodicity, safety and reliable. The battery can be manufacture din multiple specifications such as the button type or the columned type.

Description

With the composite material covered with nano surface is the lithium secondary battery of positive active material
The invention belongs to the high-energy battery technical field, particularly make the technical field of lithium ion battery and serondary lithium battery (following general designation lithium secondary battery).
The employed positive electrode active materials of lithium ion battery mainly comprises the LiCoO of rock salt structure at present 2And LiNiO 2And LiMn with spinel structure 2O 4LiCoO wherein 2Theoretical specific capacity be 272 MAH/grams, actual specific capacity is the positive electrode active materials that is applied to the commodity lithium ion battery the earliest between 120-140 MAH/gram.Because its stable performance is easy to synthesize, therefore be widely used in now in the commodity low capacity lithium ion battery.But, because the reserves of Co are lower, therefore with LiCoO 2For the lithium ion battery of positive electrode is difficult to reduce production costs, this will become the important restraining factors of the production and the popularization of high capacity lithium ion battery.LiNiO 2Theoretical specific capacity and LiCoO 2Close, reality can utilize specific capacity to compare LiCoO 2Higher, production cost is with respect to LiCoO 2Hang down.But, synthetic single-phase LiNiO 2Very big difficulty is arranged on technology, and LiNiO 2Structure also not as LiCoO 2Stable, when overcharging, also have potential safety hazard to exist, therefore also be difficult to promote the use of at present.Mn is abundant at the occurring in nature reserves, spinelle LiMn 2O 4The relative LiNiO of synthesis technique 2Also simple, therefore, spinelle LiMn 2O 4It is the positive electrode that is hopeful most to be applied in the lithium ion battery of new generation, particularly high capacity lithium ion battery.But, LiMn 2O 4Theoretical specific capacity have only 148 MAH/grams, available height ratio capacity is at present between 100-110 MAH/gram.During at higher temperature, be in the Li of Charging state when battery operated 1-xMn 2O 4In Mn 3+Can be molten to being in the acid electrolyte, so with LiMn because of containing minor amount of water 2O 4For the battery of positive electrode active materials exists shortcoming (document 1, Electrolyte Effects on SpinelDissolution and Cathodic Capacity Losses in 4 V Li/Li such as serious self-discharge phenomenon and reversible capacity decay be too fast xMn 2O 4Rechargeable Cells:Dong H.Jang and Seung M.Oh; Journal of theElectrochemical Society rolled up the 3342nd page of the 10th phase in 1997 the 144th).In addition, because synthesis technique is comparatively complicated, the LiMnO with rock salt structure 2Also be in breadboard conceptual phase at present, do not see the report that is applied to actual battery.
By substituting Ni, Mn or Co, can improve LiNiO with element M g, Al, Ti, Ga, Mn, W 2And LiMn 2O 4Structural stability, improve the cycle performance of material or reduce LiCoO 2Production cost, but the shortcoming that element substitution or doping bring is specific capacity (document 2, the Synthesis and Characterization ofNew LiNi that has reduced positive electrode simultaneously 1-yMg yO 2Positive Electrode Materials for Lithium IonBatteries; C.Pouillerie, L.Croguennec, Ph.Biensan, P.Willmann and C.Delmas, Journal of the Electrochemical Society rolled up the 2061st page of the 6th phase in 2000 the 147th).
Positive electrode is in recent years studied trend, particularly phosphate and the pyrophosphoric acid salt that oriented polyionic transition metal salt direction develops, as LiFePO 4And LiFeP 2O 7Deng, the successful exploitation of this class positive electrode is expected to further reduce the cost of anode material for lithium-ion batteries, promotes the Development and Production of high capacity cell.But, a significant drawbacks of this class material is exactly that conductivity is lower, therefore at present also be unsuitable for preparing lithium secondary battery (document 3, the Phospho-olivine as Positive-Electrode Materials forRechargeable Lithium Batteries of high power density; A.K.Padhi, K.S.Nanjundaswamy and J.B.Goodenough; Journal of the Electrochemical Society rolled up the 1188th page of the 4th phase in 1997 the 144th).
Obviously, existing positive electrode active materials can not satisfy the requirement of producing big capacity or high power lithium secondary battery.Improve the actual specific capacity of positive electrode and improve cyclicity, need the new positive electrode of exploitation or current material is carried out modification, to improve the chemical property of material.For the reason that the capacity of lithium secondary battery reduces, it is generally acknowledged that at present the factor relevant with positive electrode has: (1) under higher charging potential, electrolyte generation decomposition and consumption falls a part of lithium, and the specific capacity of material and the cycle performance of battery are reduced; (2) under higher charged state, have active transition metal ions in the positive electrode and leave material body, enter electrolyte, reduced the active component in the positive electrode; (3) lack the state of lithium in the positive electrode degree of depth, the transition metal ions tropic rearrangement in the positive electrode, the crystal structure generation irreversible transition of material reduces the electro-chemical activity of positive electrode; (4) minor amount of water of using now that electrolyte contained makes electrolyte be acid, and the positive electrode that is alkalescence is had corrosivity.
The objective of the invention is to; carry out surface coating processing by particle or electrode surface to existing positive electrode material of lithium secondary cell; change positive electrode particle surface local CHARGE DISTRIBUTION state; thereby change the surface physics and the chemical characteristic of positive electrode active materials; make positive electrode active materials can be charged to higher current potential; improve the specific capacity and the specific energy of positive electrode; the cyclicity that guarantees material does not simultaneously reduce; thereby improve the energy density of battery; improve the charge-discharge performance of battery, a kind of lithium secondary battery with higher charge/discharge capacity and better cycle performance and security performance is provided.
The object of the present invention is achieved like this:
With through the normal positive electrode that uses of the lithium secondary battery of Nanosurface coating modification as positive electrode active materials.Clad material is semimetal, oxide or salts substances, and its particle diameter is between 0.1-200nm, and average thickness is 0.5-200nm.
Through coating the positive electrode of handling, its Surface Physical Chemistry character with coat before material compare very big change: 1) surface coating layer separates the active material and the electrolyte of internal layer, because of electrolyte decomposes the capacitance loss caused, stoped in the active material transition metal ions again when both having lowered high potential to electrolytical transfer.2) owing to coat the surface that processing occurs in active material, therefore the change in concentration in active material that causes much larger than doping in the concentration of surface of active material of the ion of surperficial clad material, thereby the structure of stabilizing material more effectively, suppress the generation of irreversible transition, improve its cyclicity.3) coating so thin layer of substance in surface of active material neither can influence the transport property of lithium ion in active material inside, also can not produce appreciable impact to its transport property in surface of active material.On the contrary, because surface coating modification is to the change of surface of active material character, can not cause electrolytical decomposition to high potential more through this surface-treated positive electrode active materials is chargeable; Because this positive electrode active materials can bear higher charging potential, have higher specific capacity and specific energy again through the positive electrode active materials of this processing.Therefore the specific capacity that has guaranteed the raising material is not a cost with the cyclicity of expendable material, has taken into account material specific capacity and circulative raising simultaneously.
Clad material of the present invention can be one or more a mixture of following various types of materials: (one) semimetal: material with carbon element.Comprise various hard carbon materials, soft material with carbon element, graphite, stone
China ink formed material and modified graphite class material.(2) oxide: by IIA-VIIIA in second to the period 6 in the periodic table of chemical element
And metal or the nonmetal formed oxide or the combined oxidation of IIB-VIB family
Thing.Be specially by Mg, Al, Si, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga,
Ge，Ba，Y，Zr，Mo，In，Sn，Ta，W，La，Pr，Nd，Sm，Eu，Gd，Tb，Dy，
Ho, Er, Tm, Yb, Lu, oxide or composite oxides that Ce forms, as MgO,
Al 2O 3，SiO 2，SnO，TiO 2，SnO 2，V 2O 5，VO 2，MnO 2，Fe 2O 3，Fe 3O 4，
LiCr 2O 4，LiAlO 2，LiCoO 2，LiNiO 2，LiMn 2O 4。(3) salts substances: Li 3PO 4, AlPO 4, Mg 3(PO 4) 2, LiMPO 4(M=Mg, Fe, Co,
Ni, Cr, Ti, or V) or LiF.
The coating of active material is handled can select one of following method according to different clad materials:
Method 1: an amount of clad material predecessor is dissolved in appropriate solvent, will joins through the active material powder of certain surface preparation then in the above-mentioned solution and constantly and stir, thing is uniformly mixed.Suitably adding hot mixt desolvates to remove.To in suitable temperature and atmosphere, heat except that the mixture that desolvates, the predecessor of clad material is decomposed, obtain the composite material covered with nano surface positive active material.
Method 2: an amount of clad material predecessor is dissolved in appropriate solvent and atomizing sprays into reative cell, to join in the reative cell through the active material powder to be coated of surface preparation and carry out fluidisation, the clad material predecessor by coating particle and atomizing that is fluidized meets and forms capsule.The collection capsule also heats in suitable temperature and atmosphere, makes the predecessor decomposition of clad material can obtain the composite material covered with nano surface positive active material.
Method 3: an amount of clad material predecessor is mixed in grinding in ball grinder with active material powder to be coated, then this mixture is heated under suitable temperature and atmosphere, make the predecessor reaction of clad material generate clad material, can obtain the composite material covered with nano surface positive active material.
Method 4: some predecessor A of an amount of clad material is dissolved in appropriate solvent, is mixed into even mixed liquor with active material powder to be coated.The solution of other predecessors B of clad material is joined in the mixed liquor in the stirring gradually, and the pH value of control mixture makes the precursor A of coated thing and the sediment that B reacts generation be coated on surface of active material.Filter through cyclic washing, the filtrate that obtains heats under suitable temperature and atmosphere, can obtain the composite material covered with nano surface positive active material.
The basic structure of lithium secondary battery of the present invention is: with Nanosurface coating modification composite material is the positive pole of positive active material, the various materials that can store up lithium are negative pole, organic or inorganic electrolyte solution or polymer dielectric or solid electrolyte are electrolyte, barrier film, collector, battery case and lead-in wire are formed.Positive pole is burn-on respectively with an end of negative pole, and lead-in wire is back to link to each other with the battery case two ends or the electrode column of mutually insulated.
Lithium secondary battery of the present invention can be made button (individual layer), cylindrical (multilaminate coiled), square various ways and specifications such as (multilayer foldings) by above-mentioned basic structure.
Lithium secondary battery reversible capacity height of the present invention, cyclicity is good, and is safe and reliable; Applicable to multiple occasion, the occasion of removable power supplys such as mobile phone, notebook computer, mobile electronic device, cordless power tool for example, and electric motor car, hybrid-power electric vehicle fields such as (comprising electric bicycle, battery-operated motor cycle, electro-tricycle).
Below in conjunction with the drawings and Examples card the present invention is further described below.
Fig. 1 is an experiment lithium secondary battery structural representation of the present invention.Wherein 1,2 is the battery case of mutual insulating, 3,4 spring leafs that are respectively positive pole and negative pole, 5, the 6 support steel discs that are respectively positive pole and negative pole, 7 is the polytetrafluoroethylene screw rod, 8 is plus plate current-collecting body, and 9 is negative current collector, and 10 is positive electrode, 11 is negative material, and 12 for soaking barrier film or the polymer dielectric that electrolyte is arranged.
Fig. 2 is with nano-MgO surface coating modification LiCoO 2Composite material is the charging and discharging curve (2.5-4.3V) in anodal first week of Experimental cell and the tenth week.
Fig. 3 is with nano-MgO surface coating modification LiCoO 2Composite material is the charging and discharging curve (2.5-4.5V) in anodal first week of Experimental cell and the tenth week.
Fig. 4 is with nano-MgO surface coating modification LiCoO 2Composite material is the charging and discharging curve (2.5-4.7V) in anodal first week of Experimental cell and the tenth week.
Fig. 5 is with nanometer Al 2O 3Surface coating modification LiCoO 2Composite material is the charging and discharging curve (3.0-4.3V) in anodal first week of Experimental cell and the tenth week.
Fig. 6 is with nanometer Al 2O 3Surface coating modification LiCoO 2Composite material is the charging and discharging curve (3.0-4.5V) in anodal first week of Experimental cell and the tenth week.
Fig. 7 is with nanometer Al 2O 3Surface coating modification LiCoO 2Composite material is the charging and discharging curve (3.0-4.8V) in anodal first week of Experimental cell and the tenth week.
Fig. 8 is with nano SnO surface coating modification LiCoO 2Composite material is the charging and discharging curve (2.5-4.3V) in anodal first week of Experimental cell and the tenth week.
Fig. 9 is with nano SnO surface coating modification LiCoO 2Composite material is the charging and discharging curve (2.5-4.5V) in anodal first week of Experimental cell and the tenth week.
Figure 10 is with nanometer SiO 2Surface coating modification LiCoO 2Composite material is the charging and discharging curve (3.0-4.5V) in anodal first week of Experimental cell and the tenth week.
Figure 11 is with nanometer LiMgPO 4Surface coating modification LiCoO 2Composite material is the charging and discharging curve (2.5-4.3V) in anodal first week of Experimental cell and the tenth week.
Figure 12 is with nanometer LiMgPO 4Surface coating modification LiCoO 2Composite material is the charging and discharging curve (2.5-4.5V) in anodal first week of Experimental cell and the tenth week.
Figure 13 is with nanometer LiMgPO 4Surface coating modification LiCoO 2Composite material is the charging and discharging curve (2.5-4.7V) in anodal first week of Experimental cell and the tenth week.
Figure 14 is with nanometer LiFePO 4Surface coating modification LiCoO 2Composite material is the charging and discharging curve (2.5-4.7V) in anodal first week of Experimental cell and the tenth week.
Figure 15 is with nanometer AlPO 4Surface coating modification LiCoO 2Composite material is the charging and discharging curve (2.5-4.3V) in anodal first week of Experimental cell and the tenth week.
Figure 16 is with nanometer AlPO 4Surface coating modification LiCoO 2Composite material is the charging and discharging curve (2.5-4.5V) in anodal first week of Experimental cell and the tenth week.
Figure 17 is with nanometer LiFePO 4Surface coating modification LiCoO 2Composite material is the charging and discharging curve (2.5-4.7V) in anodal first week of Experimental cell and the tenth week.
Figure 18 is with nanometer C surface coating modification LiCoO 2Composite material is the charging and discharging curve (2.5-4.7V) in anodal first week of Experimental cell and the tenth week.
Figure 19 is with nanometer C surface coating modification LiFePO 4Composite material is the charging and discharging curve (2.5-4.5V) in anodal first week of Experimental cell and the tenth week.
Embodiment 1:
For the chemical property of lithium secondary battery of the present invention is described, adopt an Experimental cell as illustration.Its structure is seen Fig. 1, and battery is at H 2O content is lower than and is assembled in the glove box that is full of argon gas of 1.0ppm.Electrolyte is 1M LiPF 6Be dissolved in the mixed solvent of vinyl carbonate and diethyl carbonate (volume ratio is 1: 1).The coating of positive electrode active materials is handled and is adopted said method 4.To carry out the LiCoO of Nanosurface coating modification with MgO 2(coating thickness is 10nm; LiCoO 2The powder granule diameter is 5 μ m), the cyclohexane solution of acetylene black and 5%PVDF (Kynoar) mixes the formation slurry at normal temperatures and pressures, evenly be coated on the aluminum substrates.The gained film thickness is between 5-40 μ m.With the film that obtains at 150 ℃ down after the oven dry, at 20Kg/cm 2Pressure under compress, continue 150 ℃ of oven dry 12 hours down, then film being cut into area is 1cm 2Thin rounded flakes as positive plate.The weight ratio of positive plate upper electrode material each several part is 85: 10: 5.The method for making of negative plate is similar to positive plate, with the cyclohexane solution of native graphite, acetylene black and Kynoar, mixes forming composite mortar at normal temperatures and pressures, is coated in equably on the Copper Foil as collector, and the gained film thickness is between 2-20 μ m.Make it 150 ℃ of oven dry down, at pressure 20Kg/cm then 2Under compress, continued between 150 ℃ oven dry 12 hours.The weight ratio of the negative material after the oven dry (native graphite), acetylene black and binding agent is about 85: 10: 5, and it is 1cm that the film of gained is cut into area 2Disk as negative plate.
After the battery material of all except that electrolyte drying among Fig. 1, in being full of the glove box of argon gas by the Experimental cell that is assembled into shown in Figure 1.Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.Current density is 0.2mA/cm 2, the charging cut-ff voltage is 4.3, discharge cut-off voltage is 2.5V.The battery charging and discharging data are listed in the table 1.
For explanation through the discharge and recharge characteristics of Nanosurface coating modification composite positive pole with respect to lithium, in Fig. 2, listed by the simulated battery of Nanosurface coating modification composite positive pole assembling charging and discharging curve in the 1st week and the 10th week.The assembling of simulated battery and structure and aforesaid battery are identical, and just negative pole is changed to metallic lithium foil.The current density of charge and discharge cycles test is 0.2mA/cm 2, the charging cut-ff voltage is 4.3V, discharge cut-off voltage is 2.5V.
Embodiment 2
To carry out the LiCoO of surface coating modification (employing method 4) with nano-MgO 2(average thickness of coating is 10nm to composite positive pole, LiCoO 2The average grain diameter of powder is 5 μ m), the cyclohexane solution of acetylene black and 5%PVDF mixes the formation slurry at normal temperatures and pressures, evenly is coated on the aluminum substrates the about 5-40 μ of the film thickness of gained m.All the other anodal preparation processes are with embodiment 1.
The method of negative pole preparation is with embodiment 1.The assembling of simulated battery is with embodiment 1.The current density of charge and discharge cycles test is 0.2mA/cm 2, the charging cut-ff voltage is 4.5V, discharge cut-off voltage is 2.5V.Charging and discharging curve is seen Fig. 3.Discharging and recharging data lists in the table 1.
Embodiment 3
To carry out the LiCoO of surface coating modification (employing method 4) with nano-MgO 2(average thickness of coating is 10nm to composite positive pole, LiCoO 2The average grain diameter of powder is 5 μ m), the cyclohexane solution of acetylene black and 5%PVDF mixes the formation slurry at normal temperatures and pressures, on even coating and the aluminum substrates, the film thickness 5-40 μ m of gained.All the other anodal preparation processes are with embodiment 1.
The method of negative pole preparation is with embodiment 1.The assembling of simulated battery is with embodiment 1.The current density of charge and discharge cycles test is 0.2mA/cm 2, the charging cut-ff voltage is 4.7V, discharge cut-off voltage is 2.5V.Charging and discharging curve is seen Fig. 4.Discharging and recharging data lists in the table 1.
Embodiment 4
Will be with nanometer Al 2O 3Carry out the LiCoO of surface coating modification (employing method 4) 2(average thickness of coating is 5nm to composite positive pole, LiCoO 2The average grain diameter of powder is 5 μ m), the cyclohexane solution of acetylene black and 5%PVDF mixes the formation slurry at normal temperatures and pressures, evenly is coated on the aluminum substrates the about 5-40 μ of the film thickness of gained m.All the other anodal preparation processes are with embodiment 1.
The method of negative pole preparation is with embodiment 1.Use polyacrylonitrile+LiClO 4(20: 5: 45: 30 weight ratios) assembling of polymer dielectric simulated battery was with embodiment 1 for+propylene carbonate+vinyl carbonate.The current density of charge and discharge cycles test is 0.2mA/cm 2, the charging cut-ff voltage is 4.3V, discharge cut-off voltage is 3.0V.Charging and discharging curve is seen Fig. 5.Discharging and recharging data lists in the table 1.
Embodiment 5
Nanometer Al 2O 3The LiCoO of surface coating modification (employing method 4) 2(average thickness of coating is 2nm to composite positive pole, LiCoO 2The average grain diameter of powder is 5 μ m), the cyclohexane solution of acetylene black and 5%PVDF mixes the formation slurry at normal temperatures and pressures, on even coating and the aluminum substrates, the about 5-40 μ of the film thickness of gained m.All the other anodal preparation processes are with embodiment 1.
The method of negative pole preparation is with embodiment 1.Use polyacrylonitrile+LiClO 4+ propylene carbonate+vinyl carbonate (20: 5: 45: 30 weight ratios) polymer dielectric.The assembling of simulated battery is with embodiment 1.The current density of charge and discharge cycles test is 0.2mA/cm 2, the charging cut-ff voltage is 4.5V, cut-ff voltage is 3.0V.Charging and discharging curve is seen Fig. 6.Discharging and recharging data lists in the table 1.
Embodiment 6
Nanometer Al 2O 3The LiCoO of surface coating modification (employing method 4) 2(average thickness of coating is 0.5nm to composite positive pole, the average grain diameter of LiCoO2 powder is 5 μ m), the cyclohexane solution of acetylene black and 5%PVDF mixes the formation slurry at normal temperatures and pressures, on even coating and the aluminum substrates, and the about 5-40 μ of the film thickness of gained m.All the other anodal preparation processes are with embodiment 1.
The method of negative pole preparation is with embodiment 1.Use polyacrylonitrile+LiClO 4+ propylene carbonate+vinyl carbonate (20: 5: 45: 30 weight ratios) polymer dielectric.The assembling of simulated battery is with embodiment 1.The current density of charge and discharge cycles test is 0.2mA/cm 2, the charging cut-ff voltage is 4.8V, discharge cut-off voltage is 3.0V.Charging and discharging curve is seen Fig. 7.Discharging and recharging data lists in the table 1.
Embodiment 7
The LiCoO of nano SnO surface coating modification (employing method 3) 2(average thickness of coating is 50nm to composite positive pole, LiCoO 2The average grain diameter of powder is 5 μ m), the cyclohexane solution of acetylene black and 5%PVDF mixes the formation slurry at normal temperatures and pressures, on even coating and the aluminum substrates, the about 5-40 μ of the film thickness of gained m.All the other anodal preparation processes together
Embodiment 1.
The method of negative pole preparation is with embodiment 1.The assembling of simulated battery is put with embodiment 1.The current density of electricity loop test is 0.2mA/cm 2, the charging cut-ff voltage is 4.3V, discharge cut-off voltage is 2.5V.Charging and discharging curve is seen Fig. 8.Discharging and recharging data lists in the table 1.
Embodiment 8
The LiCoO of nano SnO surface coating modification (employing method 3) 2(average thickness of coating is 50nm to composite positive pole, LiCoO 2The average grain diameter of powder is 5 μ m), the cyclohexane solution of acetylene black and 5%PVDF mixes the formation slurry at normal temperatures and pressures, on even coating and the aluminum substrates, the about 5-40 μ of the film thickness of gained m.All the other anodal preparation processes together
Embodiment 1.
The method of negative pole preparation is with embodiment 1.The assembling of simulated battery is with embodiment 1.The current density of electricity loop test is 0.2mA/cm 2, the charging cut-ff voltage is 4.5V, discharge cut-off voltage is 2.5V.Charging and discharging curve is seen Fig. 9.Discharging and recharging data lists in the table 1.
Embodiment 9
Nanometer SiO 2The LiCoO of surface coating modification (employing method 2) 2(average thickness of coating is 5nm to composite positive pole, LiCoO 2The average grain diameter of powder is 5 μ m), the cyclohexane solution of acetylene black and 5%PVDF mixes the formation slurry at normal temperatures and pressures, on even coating and the aluminum substrates, the about 5-40 μ of the film thickness of gained m.All the other anodal preparation processes together
Embodiment 1.
The method of negative pole preparation is with embodiment 1.The assembling of simulated battery is with embodiment 1.The current density of charge and discharge cycles test is 0.2mA/cm 2, the charging cut-ff voltage is 4.5V, discharge cut-off voltage is 3.0V.Charging and discharging curve is seen Figure 10.Discharging and recharging data lists in the table 1.
Embodiment 10
Nanometer LiMgPO 4The LiCoO of surface coating modification (employing method 4) 2(average thickness of coating is 20nm to composite positive pole, LiCoO 2The average grain diameter of powder is 5 μ m), the cyclohexane solution of acetylene black and 5%PVDF mixes the formation slurry at normal temperatures and pressures, on even coating and the aluminum substrates, the about 5-40 μ of the film thickness of gained m.All the other anodal preparation processes are with embodiment 1.
The method of negative pole preparation is with embodiment 1.The assembling of simulated battery is with embodiment 1.The current density of charge and discharge cycles test is 0.2mA/cm 2, the charging cut-ff voltage is 4.3V, discharge cut-off voltage is 2.5V.Charging and discharging curve is seen Figure 11.Discharging and recharging data lists in the table 1.
Embodiment 11
Will be with nanometer LiMgPO 4Carry out the LiCoO of surface coating modification (employing method 4) 2(average thickness of coating is 30nm to composite positive pole, LiCoO 2The average grain diameter of powder is 5 μ m), the cyclohexane solution of acetylene black and 5%PVDF mixes the formation slurry at normal temperatures and pressures, evenly on coating and the aluminum substrates, the about 5-40 μ of the film thickness of gained m.All the other anodal preparation processes are with embodiment 1.
The method of negative pole preparation is with embodiment 1.The assembling of simulated battery is with embodiment 1.The current density of charge and discharge cycles test is 0.2mA/cm 2, the charging cut-ff voltage is the 4.5V discharge, discharge cut-off voltage is 2.5V.Charging and discharging curve is seen Figure 12.Discharging and recharging data lists in the table 1.
Embodiment 12
Will be with nanometer LiMgPO 4Carry out the LiCoO of surface coating modification (employing method 4) 2(average thickness of coating is 10nm to composite positive pole, LiCoO 2The average grain diameter of powder is 5 μ m), the cyclohexane solution of acetylene black and 5%PVDF mixes the formation slurry at normal temperatures and pressures, on even coating and the aluminum substrates, the about 5-40 μ of the film thickness of gained m.All the other anodal preparation processes are with embodiment 1.
The method of negative pole preparation is with embodiment 1.Discharging and recharging data lists in the table 1.The assembling of simulated battery is with embodiment 1.The current density of charge and discharge cycles test is 0.2mA/cm 2, the charging cut-ff voltage is 4.7V, discharge cut-off voltage is 2.5V.Charging and discharging curve is seen Figure 13.
Embodiment 13
Nanometer LiFePO 4The LiCoO of surface coating modification (employing method 4) 2(average thickness of coating is 40nm to composite positive pole, LiCoO 2The average grain diameter of powder is 5 μ m), the cyclohexane solution of acetylene black and 5%PVDF mixes the formation slurry at normal temperatures and pressures, evenly is coated on the aluminum substrates the about 5-40 μ of the film thickness of gained m.All the other anodal preparation processes are with embodiment 1.
The method of negative pole preparation is with embodiment 1.The assembling of simulated battery is with embodiment 1.The current density of charge and discharge cycles test is 0.2mA/cm 2, the charging cut-ff voltage is 4.7V, discharge cut-off voltage is 2.5V.Charging and discharging curve is seen Figure 14.Discharging and recharging data lists in the table 1.
Embodiment 14
Nanometer AlPO 4The LiCoO of surface coating modification (employing method 4) 2(average thickness of coating is 2nm to composite positive pole, LiCoO 2The average grain diameter of powder is 5 μ m), the cyclohexane solution of acetylene black and 5%PVDF mixes the formation slurry at normal temperatures and pressures, on even coating and the aluminum substrates, the about 5-40 μ of the film thickness of gained m.All the other anodal preparation processes are with embodiment 1.
The method of negative pole preparation is with embodiment 1.The assembling of simulated battery is with embodiment 1.The current density of charge and discharge cycles test is 0.2mA/cm 2, the charging cut-ff voltage is 4.3V, the electric cut-ff voltage that discharges is 2.5V.Charging and discharging curve is seen Figure 15.Discharging and recharging data lists in the table 1.
Embodiment 15
Nanometer AlPO 4The LiCoO of surface coating modification (employing method 4) 2(average thickness of coating is 1nm to composite positive pole, LiCoO 2The average grain diameter of powder is 5 μ m), the cyclohexane solution of acetylene black and 5%PVDF mixes the formation slurry at normal temperatures and pressures, on even coating and the aluminum substrates, the about 5-40 μ of the film thickness of gained m.All the other anodal preparation processes are with embodiment 1.
The method of negative pole preparation is with embodiment 1.The assembling of simulated battery is with embodiment 1.The current density of charge and discharge cycles test is 0.2mA/cm 2, the charging cut-ff voltage is 4.5V, discharge cut-off voltage is 2.5V.Charging and discharging curve is seen Figure 16.Discharging and recharging data lists in the table 1.
Embodiment 16
Nanometer LiFePO 4The LiCoO of surface coating modification (employing method 4) 2(average thickness of coating is 10nm to composite positive pole, LiCoO 2The average grain diameter of powder is 5 μ m), the cyclohexane solution of acetylene black and 5%PVDF mixes the formation slurry at normal temperatures and pressures, on even coating and the aluminum substrates, the about 5-40 μ of the film thickness of gained m.All the other anodal preparation processes are with embodiment 1.
The method of negative pole preparation is with embodiment 1.The assembling of simulated battery is with embodiment 1.The current density of charge and discharge cycles test is 0.2mA/cm 2, the charging cut-ff voltage is 4.7V, discharge cut-off voltage is 2.5V.Charging and discharging curve is seen Figure 17.Discharging and recharging data lists in the table 1.
Embodiment 17
The LiCoO of nanometer C surface coating modification (employing method 1) 2(average thickness of coating is 50nm to composite positive pole, LiCoO 2The average grain diameter of powder is 5 μ m), the cyclohexane solution of acetylene black and 5%PVDF mixes the formation slurry at normal temperatures and pressures, on even coating and the aluminum substrates, the about 5-40 μ of the film thickness of gained m.All the other anodal preparation processes are with embodiment 1.
The method of negative pole preparation is with embodiment 1.The assembling of simulated battery is with embodiment 1.The current density of charge and discharge cycles test is 0.2mA/cm 2, the charging cut-ff voltage is 4.7V, discharge cut-off voltage is 2.5V.Charging and discharging curve is seen Figure 18.Discharging and recharging data lists in the table 1.
Embodiment 18
The LiFPO of nanometer C surface coating modification (employing method 2) 4(average thickness of coating is 100nm to composite positive pole, LiCoO 2The average grain diameter of powder is 5 μ m), the cyclohexane solution of acetylene black and 5%PVDF mixes the formation slurry at normal temperatures and pressures, on even coating and the aluminum substrates, the about 5-40 μ of the film thickness of gained m.All the other anodal preparation processes together
Embodiment 1.
The method of negative pole preparation is with embodiment 1.The assembling of simulated battery is with embodiment 1.The current density of charge and discharge cycles test is 0.2mA/cm 2, the charging cut-ff voltage is 4.7V, discharge cut-off voltage is 2.5V.Charging and discharging curve is seen Figure 19.Discharging and recharging data lists in the table 1.
Table 1. is that the Experimental cell of positive active material discharges and recharges tables of data with the surface coating modification composite material
Clad material Active material Charging voltage Discharge voltage The initial discharge specific capacity Loop parameter
??MgO ????LiCoO 2 ????4.5 ????2.5 ????182 ????0.033
??MgO ????LiCoO 2 ????4.7 ????2.5 ????207 ????0.019
??Al 2O 3 ????LiCoO 2 ????4.3 ????3.0 ????135 ????0.052
??Al 2O 3 ????LiCoO 2 ????4.5 ????3.0 ????192 ????0.001
??Al 2O 3 ????LiCoO 2 ????4.8 ????3.0 ????207 ????0.034
??SnO ????LiCoO 2 ????4.3 ????2.5 ????151 ????0.060
??SnO ????LiCoO 2 ????4.5 ????2.5 ????183 ????0.005
??SnO ????LiCoO 2 ????4.7 ????2.5 ????205 ????0.078
??SiO 2 ????LiCoO 2 ????4.5 ????3.0 ????188 ????0.112
??LiPO 4 ????LiCoO 2 ????4.3 ????2.5 ????145 ????0.025
??LiPO 4 ????LiCoO 2 ????4.5 ????2.5 ????178 ????0.031
??LiPO 4 ????LiCoO 2 ????4.7 ????2.5 ????204 ????0.051
??LiMgPO 4 ????LiCoO 2 ????4.3 ????2.5 ????138 ????0.029
??LiMgPO 4 ????LiCoO 2 ????4.5 ????2.5 ????170 ????0.006
??LiMgPO 4 ????LiCoO 2 ????4.7 ????2.5 ????198 ????0.061
??LiFePO 4 ????LiCoO 2 ????4.5 ????2.5 ????163 ????0.012
??AlPO 4 ????LiCoO 2 ????4.3 ????2.5 ????148 ????0.054
??AlPO 4 ????LiCoO 2 ????4.5 ????2.5 ????164 ????0.030
??AlPO 4 ????LiCoO 2 ????4.7 ????2.5 ????210 ????0.103
??C ????LiCoO 2 ????4.3 ????2.5 ????162 ????0.013
??MgO ????LiNiO 2 ????4.3 ????2.5 ????176 ????0.053
??MgO ????LiNiO 2 ????4.5 ????2.5 ????224 ????0.106
??Al 2O 3 ????LiNiO 2 ????4.3 ????2.5 ????177 ????0.057
??Al 2O 3 ????LiNiO 2 ????4.5 ????2.5 ????232 ????0.114
??SnO ????LiNiO 2 ????4.5 ????2.5 ????221 ????0.089
??LiMgPO 4 ????LiNiO 2 ????4.5 ????2.5 ????228 ????0.093
??C ????LiNiO 2 ????4.3 ????2.5 ????183 ????0.021
??MgO ?LiNi 0.8Co 0.2O 2 ????4.3 ????2.5 ????166 ????0.025
??MgO ?LiNi 0.8Co 0.2O 2 ????4.5 ????2.5 ????206 ????0.036
??Al 2O 3 ?LiNi 0.8Co 0.2O 2 ????4.3 ????2.5 ????178 ????0.043
??Al 2O 3 ?LiNi 0.8Co 0.2O 2 ????4.5 ????2.5 ????212 ????0.063
??SnO ?LiNi 0.8Co 0.2O 2 ????4.5 ????2.5 ????218 ????0.072
??LiMgPO 4 ?LiNi 0.8Co 0.2O 2 ????4.5 ????2.5 ????220 ????0.092
??C ?LiNi 0.8Co 0.2O 2 ????4.5 ????2.5 ????215 ????0.039
??AlPO 4 ?LiNi 0.8Co 0.2O 2 ????4.5 ????2.5 ????222 ????0.106
??Li 3PO 4 ?LiNi 0.8Co 0.2O 2 ????4.5 ????2.5 ????228 ????0.096
????MgO ????LiMn 2O 4 ????4.5 ????2.5 ????127 ????0.023 *
????Al 2O 3 ????LiMn 2O 4 ????4.5 ????2.5 ????131 ????0.016 *
????SnO ????LiMn 2O 4 ????4.5 ????2.5 ????124 ????0.011 *
????LiMgPO 4 ????LiMn 2O 4 ????4.5 ????2.5 ????128 ????0.013 *
????C ????LiMn 2O 4 ????4.5 ????2.5 ????130 ????0.025 *
????AlPO 4 ????LiMn 2O 4 ????4.5 ????2.5 ????123 ????0.010 *
????Li 3PO 4 ????LiMn 2O 4 ????4.5 ????2.5 ????129 ????0.026 *
????C ????LiFePO 4 ????4.0 ????2.5 ????125 ????0.011
????TiO 2 ????LiNiO 2 ????4.5 ????2.5 ????195 ????0.135
????SnO 2 ????LiNiO 2 ????4.5 ????2.5 ????187 ????0.126
????V 2O 5 ????LiNiO 2 ????4.5 ????2.5 ????192 ????0.113
????MnO 2 ????LiCoO 2 ????4.5 ????2.5 ????168 ????0.057
????Fe 2O 3 ????LiMn 2O 4 ????4.5 ????2.5 ????132 ????0.063 *
????LiCr 2O 4 ????LiMn 2O 4 ????4.5 ????2.5 ????135 ????0.059 *
????LiAlO 2 ????LiCoO 2 ????4.5 ????2.5 ????166 ????0.025
????LiCoO 2 ????LiMn 2O 4 ????4.5 ????2.5 ????138 ????0.116 *
????LiNiO 2 ????LiMn 2O 4 ????4.5 ????2.5 ????135 ????0.125 *
????LiMn 2O 4 ????LiCoO 2 ????4.5 ????2.5 ????178 ????0.035
????Mg 3(PO 4) 2 ????LiMn 2O 4 ????4.5 ????2.5 ????137 ????0.104 *
????LiCoPO 4 ????LiMn 2O 4 ????4.5 ????2.5 ????133 ????0.095 *
????LiNiPO 4 ????LiCoO 2 ????4.5 ????2.5 ????175 ????0.024
????LiVPO 4 ????LiCoO 2 ????4.5 ????2.5 ????173 ????0.037
????LiTiPO 4 ????LiCoO 2 ????4.5 ????2.5 ????169 ????0.025
????LiF ????LiMn 2O 4 ????4.5 ????2.5 ????136 ????0.103 *
Annotate: 1) initial specific volume value is based on positive electrode active materials (containing clad material) and calculates gained, and promptly actual the 1st week discharge is held
Amount is divided by the positive electrode active materials quality.The cyclicity parameter is meant that the specific discharge capacity in the 1st week deducts putting of the 10th week
Electricity specific capacity gained difference is divided by the specific discharge capacity in the 1st week;
2) voltage unit is " volt "; Bodge is " MAH/gram "; 3) measure temperature and be generally 25-30 ℃; Have *It is 55 ℃ that number person measures temperature.

Claims (5)

1. with the composite material covered with nano surface lithium secondary battery of positive active material, comprise the negative pole, the organic or inorganic electrolyte that store up lithium in every way, there are the barrier film of electrolyte solution or polymer dielectric or solid electrolyte to separate by immersion between positive pole and the negative pole, be encapsulated in the battery case, link to each other with the battery case or the electrode column of mutually insulated respectively from lead anodal and that negative pole is drawn, it is characterized in that: positive electrode active material powder is handled through the Nanosurface coating modification; Encapsulated material is present positive electrode active materials general in lithium secondary battery; Clad material is semimetal, oxide or salts substances, can be the mixture of one or more clad materials wherein; The coating layer average thickness is 0.5-200nm, and particle diameter is 0.1-200nm; Evenly film is made in coating or roll-in on conductive carrier will to mix the composite mortar that forms with binding agent, conductive agent by Nanosurface coating modification composite material, after the film oven dry, through densification, with the conventional method oven dry, be cut into required form by the battery specification and get final product again.
2. by claim 1,2 described be the lithium secondary battery of positive active material with the composite material covered with nano surface, it is characterized in that: described semimetal is a material with carbon element, is specially various hard carbon materials, soft material with carbon element, graphite, graphitized material or modified graphite class material.
3. described by claim 1 is the lithium secondary battery of positive active material with the composite material covered with nano surface, it is characterized in that: described oxide is by the metal of IIA-VIIIA in second to the period 6 in the periodic table of chemical element and IIB-VIB family, nonmetal formed oxide or composite oxides.
4. by claim 1,4 described be the lithium secondary battery of positive active material with the composite material covered with nano surface, it is characterized in that: described oxide is for by Mg, Al, Si, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, Ge, Ba, Y, Zr, Mo, In, Sn, Ta, W, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, oxide or composite oxides that Ce forms.
5. described by claim 1 is the lithium secondary battery of positive active material with the composite material covered with nano surface, it is characterized in that: described salts substances is Li 3PO 4, AlPO 4, Mg 3(PO 4) 2, LiMPO 4(M=Mg, Fe, Co, Ni, Cr, Ti, or V) or LiF.
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