CN1262533A - Secondary lithium battery - Google Patents

Secondary lithium battery Download PDF

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CN1262533A
CN1262533A CN99100282A CN99100282A CN1262533A CN 1262533 A CN1262533 A CN 1262533A CN 99100282 A CN99100282 A CN 99100282A CN 99100282 A CN99100282 A CN 99100282A CN 1262533 A CN1262533 A CN 1262533A
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nanometer
charging
lithium
discharge
discharge capacities
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李晶泽
黄学杰
李泓
陈立泉
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Institute of Physics of CAS
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    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

A new-type ordinary-temp secondary lithium battery features that its cathode or anode contains at least one of active substances A, B, C, D, E, F and G, where A is a nm-class sulfur, sulfide, polysulfide, or sulfide containing Li, B is nm-class bromide, or bromide containing Li, C is nm-class idione, idide, or idide containing Li, D is nm-class nitride, or nitride containing Li, E is nm-class oxide, or oxide containing Li, F is nm-class selenium, selenide, or selenide containing Li and G is nm-class interhalogen compound. Their granularity is 500 nm-1nm. Its advantages are different working voltages, high cycle nature and reversable capacity and high-current charge and discharge.

Description

A kind of serondary lithium battery
The present invention relates to the high-energy battery technical field, particularly relate to a kind of serondary lithium battery that is applicable to room temperature.
Because the lithium metal as Anode of lithium cell has high electrochemical equivalent, thereby lithium battery generally has very high specific energy.Just cause extensive attention in mid-term in this century, caused the very fast commercialization of disposable lithium-battery., the development of serondary lithium battery but relatively slowly.Studies show that dendritic growth appears in lithium metal anode in charge and discharge process, make internal short-circuit of battery, cause battery burning even blast when serious.Although the lithium alloy of discovering subsequently can improve its fail safe, its cycle performance fails to make a breakthrough always.As list of references [1]: A Bolahanmu, electrochemistry communication, 138 volumes, 1233 pages, 1993
Narrate in (K.M.Abraham, Electrochimica.Acta., Vol.138,1233 (1993)).
For obtaining than high-energy-density, corresponding cathode material must be able to provide the electrode potential of calibration and higher specific capacity.Materials such as fluorine, chlorine, oxygen, though theoretical specific energy is higher, toxicity is big, corrosivity is strong, is again gas, is difficult to handle; Sulphur also has the high theoretical specific energy, but at room temperature its activity is too low.Therefore, the disposable lithium-battery cathode material mainly is liquid such as solid fluoride, chloride, iodide, oxide, sulfide and sulfur dioxide, chlorosulfuric acid, thionyl chloride.Corresponding serondary lithium battery cathode material also derives from above-mentioned a few class material.As list of references [2]: En Qige, Electroanalytical Chemistry, 72 volumes, 1-31 page or leaf, 1976
Narrate in (G.Eich inger, J.O.Besenhard, J.Electroanal.Chem., Vol72,1-31 (1976)).
1980, Armand proposes serondary lithium battery can adopt " rocking chair type " battery system (" lithium ion " battery afterwards was otherwise known as), be that the anode and cathode active material all adopts embedding compound (intercalationcompounds), this compounds can be reversible storage and exchange lithium ion, thereby avoid using lithium metal or lithium alloy.Initial stage is adopted LiWO 2And Li 6Fe 2O 3Deng embedding compound as active material of positive electrode, but its energy density reduces greatly.Through the effort in 10 years, in March, 1989, Japanese Sony Corporation applied for that employing carbon makes active material of positive electrode, LiCoO 2Make the patent of the serondary lithium battery of active material of cathode, and in 1992 at first with its commercialization, as document [3] Bu Lunuo, electrochemistry can will, 139 volumes, 2776 pages, 1992
(Bruno?Scrosati，J.Electrochem.Soc.，Vol.139，2776(1992))。
From then on, serondary lithium battery begins to develop rapidly.The material with carbon element of various ways such as petroleum coke, carbon fiber, RESEARCH OF PYROCARBON, native graphite, Delanium extensively is elected to be the active material of positive electrode of serondary lithium battery.Remove LiCoO 2Outward, LiMn 2O 4, LiNiO 2Wait other transition metal oxides that contain lithium also to be expected to cathode material as the commercialization serondary lithium battery.
But anode uses carbon, and negative electrode uses the serondary lithium battery of lithium-containing transition metal oxide still can not satisfy the demand of high-performance secondary cell.For example power density is not high enough, the particularly not big electric current quick charge of ability, and specific energy is not high enough, and cryogenic property remains further to be improved or the like.
Simultaneously, the operating voltage of lithium ion battery is 3.6V, and the serondary lithium battery to different voltage series also has urgent demand on the market.
In recent years, because nano material has some special nature, also caused extensive concern in field of batteries.It is reported LiMn 2O 4, TiS 2, TiO 2Nanotube, nanofiber or nano composite material have all shown more excellent chemical property, as higher specific power and specific capacity.As document [4] Xi swamp, electrochemistry meeting will, 144 volumes, 1923 pages, 1997 (M.Nishizawa, et.al., J.Electrochem.Soc., Vol.144,1923 (1997)).
The objective of the invention is to overcome the shortcoming and defect of above-mentioned known technology.Performance for the power density, specific energy and the anti-big electric current fast charging and discharging that improve serondary lithium battery; In order to make serondary lithium battery that cyclicity preferably be arranged, higher fail safe further improves battery performance at low temperatures; And the scope of application that enlarges serondary lithium battery, thereby provide a kind of novel serondary lithium battery.
The object of the present invention is achieved like this:
Serondary lithium battery provided by the invention comprises anode, negative electrode, organic electrolyte solution or solid electrolyte composition, and the structure that each several part is enclosed in the battery case is identical with known technology.It is characterized in that at least one side of described anode and negative electrode is contained the disperse phase nanometer combined electrode material.The disperse phase nanometer combined electrode material comprises electrode active material and the disperse means two parts that can store, discharge lithium, the granularity of electrode active material wherein is between 500nm～1nm, its shared percentage by weight in the disperse phase nano composite material is 95% to 30%, and surplus is disperse means.
Having at least a kind of in the electrode active material that the disperse phase nanometer combined electrode material is comprised is (A) nanometer sulphur, nanometer sulfide, nanometer polysulfide and the nanometer sulfide that contains lithium; (B) nanometer bromide and contain the nanometer bromide of lithium; (C) nanometer iodine, nanometer iodide and contain the nanometer iodide of lithium; (D) nano nitride and contain the nano nitride of lithium; (E) nano-oxide and contain the nano-oxide of lithium; (F) nanometer selenium, nanometer selenides and contain the nanometer selenides of lithium; Or (G) compound between the nanometer halogen.
Wherein said electrode active material (A) is: nanometer sulphur, nanometer sulfide, nanometer polysulfide and contain the nanometer sulfide of lithium, wherein nanometer sulfide, nanometer polysulfide and the nanometer sulfide that contains lithium are the compounds that metallic element Bi, Si, Sb, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pb, Ag, Nb, Mo, Sn, W, Cd, Zr and sulphur form.
Wherein said electrode active material (B) nanometer bromide and the nanometer bromide that contains lithium are the compounds that metallic element Li, Cu, Ag, Pb and bromine form.
Wherein said electrode active material (C) is: nanometer iodine, nanometer iodide and contain the nanometer iodide of lithium, wherein nanometer iodide and the nanometer iodide that contain lithium are compounds that metallic element Li, Cu, Ag, Pb and iodine form.
Wherein said electrode active material (D) nano nitride and the nano nitride that contains lithium are the compounds that metallic element Mn, Fe, Co, Ni, Cu and nitrogen form.
Wherein said electrode active material (E) nano-oxide and the nano-oxide that contains lithium are the compounds that metal element Ti, V, Fe, Co, Cu, Pb, Bi, Cr, W, Mo, Mn, Ni and oxygen form.
Wherein said electrode active material (F) is: nanometer selenium, nanometer selenides and contain the nanometer selenides of lithium, wherein nanometer selenides and the nanometer selenides that contains lithium are the compounds that metal element Ti, V, Pb, Nb, Zr and selenium form.
Wherein said electrode active material (G) nanometer interhalogen compounds is IF 3, ICl, IBr.
Disperse means comprise two parts, a part has been the conductive additive of conduction and peptizaiton, its granularity is 1nm～20um, as Cu, Al, Ni, Fe, Ag powder, acetylene black, carbon black, graphite powder, carbon fiber, mesocarbon bead or conducting polymers such as polyaniline, polypyrrole, its percentage by weight shared in the disperse phase nano composite material is 0% to 60%.
Another part has been bonding and adhesive peptizaiton, can be polytetrafluoroethylene, Kynoar, and polyacrylonitrile, poly(ethylene oxide), ethylene-propylene rubber, its percentage by weight shared in the disperse phase nano composite material is 2%-40%.
Because the electrode potential of the disperse phase nano composite material that serondary lithium battery of the present invention adopted generally is lower than LiCoO 2, LiMn 2O 4, LiNiO 2Wait the electrode potential of some conventional cathode materials, but the electrode potential that generally is higher than some conventional anode materials such as graphite, lithium metal, petroleum coke, so its anode of serondary lithium battery of the present invention can be made up of the disperse phase nano composite material, its negative electrode also can be made up of the disperse phase nano composite material, and perhaps two electrodes of negative and positive are formed by the disperse phase nano composite material.When negative electrode was the disperse phase nano composite material, it was lithium metal, lithium silicon alloy, lithium-aluminium alloy, Li-Pb alloy, lithium-tin alloy, LiTiO to the active material of electrode accordingly 2, the negative material of some current potentials such as graphite, carbon; When anode was the multiple platform material of disperse phase nanometer, its active material of tackling electrode mutually was LiCoO 2, LiMn 2O, LiNiO 2Or other contain the material of some current potential calibrations such as metal oxide of lithium.
Serondary lithium battery of the present invention comprises that also structures such as organic electrolyte solution, barrier film, battery case, collector, lead-in wire are the same with the known technology battery except that anode, active material of cathode.Wherein, separated by barrier film that has soaked organic electrolyte solution or polymer dielectric between negative electrode and the anode, an end of negative electrode and anode is welding lead and link to each other with the battery case two ends of mutually insulated on collector respectively.
Negative electrode among the present invention and anode preparation method are: active material and conductive additive are mixed by a certain percentage, evenly be mixed and made into the composite material slurries at normal temperatures and pressures with adhesive again.Wherein, sticking platform agent comprises solution or emulsion.For example, polytetrafluoroethylene is mixed the emulsion that forms with water; Kynoar is dissolved in the solution that cyclopentanone forms.Aforesaid composite material slurries are coated in paper tinsel as the various conductions of collector uniformly, net, porous body is on the corpus fibrosum material carriers such as (as Copper Foils, aluminium foil, nickel screen, nickel foam, carbon felt).Directly insert in the porous body after also active material and disperse means can being mixed.The gained film thickness is about 1～300 μ m, then film or porous body dried down at 100 ℃-150 ℃, and be 20Kg/cm at pressure 2Following compacting continues prepared film to be cut into different shape by the battery specification to be electrode 100 ℃-150 ℃ bakings 12 hours.
The organic electrolyte solution of serondary lithium battery of the present invention is the general electrolyte of lithium battery, can be added one or more solvable lithium salts by the mixed solvent that a kind of organic solvent or several organic solvent are formed and form.Typical organic solvent is vinyl carbonate for example, propylene carbonate, diethyl carbonate, dimethyl carbonate, the ethyl-methyl carbonic ester, dimethoxy-ethane etc., typical solvable lithium salts such as lithium perchlorate, LiBF4, lithium hexafluoro phosphate, trifluoromethyl sulfonic acid lithium, the fluosulfonic acid imide li of enjoying a double blessing, hexafluoroarsenate lithium etc.It is in 1: 1 the vinyl carbonate and diethyl carbonate that typical system is dissolved in volume ratio as 1 mole of lithium hexafluoro phosphate, and it is that 3: 7 vinyl carbonate and dimethyl carbonate is medium that 1 mole of lithium hexafluoro phosphate is dissolved in volume ratio.
The barrier film of lithium battery of the present invention is the general barrier film of serondary lithium battery, as the porous polypropylene barrier film, and porous polyethylene barrier film etc.
Advantage of the present invention:
Serondary lithium battery of the present invention can not only provide a series of different operating voltages (voltage range of selection can between 1.0V to 3.7V), has enlarged the scope of application of serondary lithium battery, and has increased diversity and popularity on electrode material is selected.Because negative electrode is or/and contain the nano active material in the anode, electrode active material has bigger specific area; And lithium ion also reduces accordingly in the diffusion depth of nano active material internal, helps the minimizing of electrode polarization degree; The high voidage of nano active material makes the solvent molecule in the electrolyte that more migration space arranged, and the real surface that has increased electrode reaction is long-pending; Simultaneously, owing to after material particle size reaches nanometer scale, produce a large amount of crystal boundaries ionic conductivity is increased, help ion transporting in electrode interior.These will cause novel serondary lithium battery higher fail safe to be arranged with than high power charging-discharging, improve the reversible capacity of serondary lithium battery.The granularity of the nano-electrode active material that the disperse phase nano composite material is comprised is much smaller than the granularity of ordinary electrode active material, in the process of storage, release lithium, the volume change of nano particle is less than the volume fraction rate of change of the particle of ordinary electrode active material, thereby nano-electrode active matter mass-energy permanent keep good electrical contact with conductive additive, collector etc., help improving the cycle life of battery.
Serondary lithium battery of the present invention is applicable to multiple occasion, and for example mobile phone, notebook computer, portable video recorder, electronic toy, cordless power tool etc. need the occasion of removable power supply, also comprise fields such as electric automobile.
Below in conjunction with drawings and Examples the present invention is done further narration.
Fig. 1 is the structural representation of button Experimental cell of the present invention.
Fig. 2 is the charging and discharging curve of the embodiment of the invention 1 Experimental cell.
Fig. 3 is the charging and discharging curve of the embodiment of the invention 2 Experimental cells.
Fig. 4 is the charging and discharging curve of the embodiment of the invention 15 Experimental cells.
The drawing of accompanying drawing 1 is described as follows:
1 is the stainless steel sealing nut; 2 is the polytetrafluoroethylene nut;
3 is the stainless steel spring sheet; 4 for being the work electrode of battery with the disperse phase nano composite material:
5 is porous polypropylene barrier film Celgard 2400 (soaking through electrolyte);
6 is metal lithium sheet to electrode: 7 for measuring lead:
[embodiment 1]
Adopt button Experimental cell rice as shown in Figure 1 to realize the present invention.It comprises stainless steel sealing nut (1), polytetrafluoroethylene nut (2), stainless steel spring sheet (3), disperse phase nanometer CuS anode (4), through the porous polypropylene barrier film Celgard 2400 (5) that electrolyte soaks, metal lithium sheet is measured lead (7) to electrode (6).Electrolyte is that 1 mole of lithium hexafluoro phosphate is dissolved in the mixed solvent of vinyl carbonate and diethyl carbonate (volume ratio is 1: 1).
Its anode composed as follows: electrode active material is a nanometer CuS powder (50nm), and the conductive additive in the disperse means uses carbon black, and the adhesive in the disperse means adopts the cyclopentanone solution of Kynoar.The preparation method is: at normal temperatures and pressures, at first nanometer CuS powder and the 0.40g carbon black with 0.40g mixes, and then the 0.20g Kynoar is dissolved in 2ml cyclopentanone solution, at last said two devices evenly is mixed and made into the composite material slurries.Composite material sizing agent evenly is coated on the Copper Foil substrate as collector the about 20 μ m of the film thickness of gained.With the film that obtains at 150 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continue again 150 ℃ of down oven dry 12 hours, then film being cut to area is 1cm 2Thin rounded flakes as disperse phase nanometer CuS composite material anode.
With thick 0.4mm, area is 1cm 2Metal lithium sheet as negative electrode.
With all battery materials among Fig. 1, except that electrolyte, dry back in the argon filling glove box 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 0.1mA/cm 2, the charging cut-ff voltage is 3.0V, discharge cut-off voltage is 1.0V.
Fig. 2 is the charging and discharging curve in the 1st week of anode described in the present embodiment and the 5th week.The electrochemistry capacitance that is calculated as active material of capacity.First all discharge capacities are 355mAh/g, and two discharge platforms are respectively at 2.1V and 1.6V; First all charging capacitys are 300mAh/g, and two charging platforms are respectively at 1.9V and 2.2V.The 5th all discharge capacities are 260mAh/g.[embodiment 2]
Preparation method such as embodiment 1, only electrode material is pressed following prescription:
With 0.95g nanometer CuS powder (50nm), the 0.03g carbon black mixes the formation slurry at normal temperatures and pressures with the solution that the 0.02g Kynoar is dissolved in 2ml cyclopentanone gained, evenly is coated on the Copper Foil substrate the about 20 μ m of gained film thickness.All the other anode preparation steps are with embodiment 1.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Fig. 3 is the charging and discharging curve in the 1st week of anode described in the present embodiment and the 5th week.First all discharge capacities are 110mAh/g, and charging capacity is 70mAh/g.The 5th all discharge capacities are 40mAh/g.[embodiment 3]
With 0.30g nanometer CuS powder (50nm), the 0.60g carbon black mixes the formation slurry at normal temperatures and pressures with the solution that the 0.10g Kynoar is dissolved in 2ml cyclopentanone gained, evenly is coated on the Copper Foil substrate the about 20 μ m of gained film thickness.All the other anode preparation steps are with embodiment 1.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 355mAh/g, and charging capacity is 310mAh/g.The 5th all discharge capacities are 270mAh/g.[embodiment 4]
The solution that 0.60g nanometer CuS powder (50nm) and 0.40g Kynoar is dissolved in 2ml cyclopentanone gained mixes the formation slurry at normal temperatures and pressures, evenly is coated on the Copper Foil substrate the about 20 μ m of gained film thickness.All the other anode preparation steps are with embodiment 1.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 87mAh/g, and charging capacity is 35mAh/g.The 5th all discharge capacities are 25mAh/g.[embodiment 5]
With 0.40g nanometer CuS powder (50nm), 0.40g graphite mixes the formation slurry at normal temperatures and pressures with the solution that the 0.20g Kynoar is dissolved in 2ml cyclopentanone gained, evenly is coated on the Copper Foil substrate the about 20 μ m of gained film thickness.All the other anode preparation steps are with embodiment 1.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 250mAh/g, and charging capacity is 200mAh/g.The 5th all discharge capacities are 160mAh/g.[embodiment 6]
With 0.30g nanometer CuS powder (50nm), 0.60g graphite mixes the formation slurry at normal temperatures and pressures with the solution that the 0.10g Kynoar is dissolved in 2ml cyclopentanone gained, evenly is coated on the Copper Foil substrate the about 20 μ m of gained film thickness.All the other anode preparation steps are with embodiment 1.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 260mAh/g, and charging capacity is 210mAh/g.The 5th all discharge capacities are 180mAh/g.[embodiment 7]
With 0.50g nanometer CuS powder (50nm), 0.40 metallic aluminium powder (99%, 5 μ m) mix the formation slurry at normal temperatures and pressures with the solution that 0.10g polyacrylonitrile (PAN) is dissolved in 2ml gamma-butyrolacton gained, evenly be coated on the Copper Foil substrate the about 20 μ m of the film thickness of gained.All the other anode preparation steps are with embodiment 1.Remove on the charging voltage and be limited to 3.0V, be limited to outside the 1.5V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 95mAh/g, and charging capacity is 60mAh/g.The 5th all discharge capacities are 40mAh/g.[embodiment 8]
With 0.40g nanometer CuS powder (50nm), 0.50g copper powder (99.9%, 5 μ m) mix the formation slurry at normal temperatures and pressures with the solution that 0.10g polyacrylonitrile (PAN) is dissolved in 2ml gamma-butyrolacton gained, evenly be coated on the Copper Foil substrate the about 20 μ m of the film thickness of gained.All the other anode preparation steps are with embodiment 1.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 113mAh/g, and charging capacity is 87mAh/g.The 5th all discharge capacities are 78mAh/g.[embodiment 9]
With 0.40g nanometer CuS powder (50nm), 0.50g metal zinc (99%, 38 μ m) mix the formation slurry at normal temperatures and pressures with the solution that 0.10g polyacrylonitrile (PAN) is dissolved in 2ml gamma-butyrolacton gained, evenly be coated on the Copper Foil substrate the about 40 μ m of the film thickness of gained.All the other anode preparation steps are with embodiment 1.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 104mAh/g, and charging capacity is 80mAh/g.The 5th all discharge capacities are 75mAh/g.[embodiment 10]
With 0.40g nanometer CuS powder (50nm), 0.50g metal nickel powder (99%, 38 μ m) mix the formation slurry at normal temperatures and pressures with the solution that 0.10g polyacrylonitrile (PAN) is dissolved in 2ml gamma-butyrolacton gained, evenly be coated with Ao on the Copper Foil substrate, the about 40 μ m of the film thickness of gained.All the other anode preparation steps are with embodiment 1.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 108mAh/g, and charging capacity is 88mAh/g.The 5th all discharge capacities are 79mAh/g.[embodiment 11]
With 0.40g nanometer CuS powder (50nm), 0.50g metal iron powder (99%, 38 μ m) mix the formation slurry at normal temperatures and pressures with the solution that 0.10g polyacrylonitrile (PAN) is dissolved in 2ml gamma-butyrolacton gained, evenly be coated on the Copper Foil substrate the about 50 μ m of the film thickness of gained.All the other anode preparation steps are with embodiment 1.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 96mAh/g, and charging capacity is 78mAh/g.The 5th all discharge capacities are 56mAh/g.[embodiment 12]
With 0.40g nanometer CuS powder (50nm), 0.50g metal antimony powder (99%, 38 μ m) mixes the formation slurry at normal temperatures and pressures with the solution that the 0.10g Kynoar is dissolved in 2ml cyclopentanone gained, evenly is coated on the Copper Foil substrate the about 20 μ m of the film thickness of gained.All the other anode preparation steps are with embodiment 1.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 90mAh/g, and charging capacity is 72mAh/g.The 5th all discharge capacities are 43mAh/g.[embodiment 13]
With 0.40g nanometer CuS powder (50nm), 0.20g copper powder (99%, 5 μ m), 0.30g acetylene black is mixed the formation slurry at normal temperatures and pressures with the solution that the 0.10g Kynoar is dissolved in 2ml cyclopentanone gained, evenly be coated on the Copper Foil substrate the about 20 μ m of the film thickness of gained.All the other anode preparation steps are with embodiment 1.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 310mAh/g, and charging capacity is 255mAh/g.The 5th all discharge capacities are 218mAh/g.[embodiment 14]
With 0.50g nanometer CuS powder (50nm), 0.20g metal nickel powder (99%, 38 μ m), 0.20g Ag powder (20nm) mixes the formation slurry at normal temperatures and pressures with the solution that the 0.10g Kynoar is dissolved in 2ml cyclopentanone gained, evenly be coated on the Copper Foil substrate the about 40 μ m of the film thickness of gained.All the other anode preparation steps are with embodiment 1.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 335mAh/g, and charging capacity is 290mAh/g.The 5th all discharge capacities are 261mAh/g.[embodiment 15]
Form identical anode by embodiment 1 described making.Other material of Experimental cell, structure, assembling and method of testing are all with embodiment 1.Current density increases to 0.8mA/cm 2, discharge and recharge cut-ff voltage with embodiment 1.
Fig. 4 is the charging and discharging curve in the 1st week of anode described in the present embodiment and the 5th week.First all discharge capacities are 300mAh/g, and charging capacity is 290mAh/g.The 5th all discharge capacities are 261mAh/g.[embodiment 16]
With 0.40g nanometer CuS powder (1nm), the 0.40g carbon black mixes the formation slurry at normal temperatures and pressures with the solution that the 0.20g Kynoar is dissolved in 2ml cyclopentanone gained, evenly is coated on the Copper Foil substrate the about 20 μ m of the film thickness of gained.All the other anode preparation steps are with embodiment 1.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 380mAh/g, and charging capacity is 320mAh/g.The 5th all discharge capacities are 280mAh/g.[embodiment 17]
With 0.40g nanometer CuS powder (100nm), the 0.40g carbon black mixes the formation slurry at normal temperatures and pressures with the solution that the 0.20g Kynoar is dissolved in 2ml cyclopentanone gained, evenly is coated on the Copper Foil substrate the about 20 μ m of the film thickness of gained.All the other anode preparation steps are with embodiment 1.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 270mAh/g, and charging capacity is 210mAh/g.The 5th all discharge capacities are 160mAh/g.[embodiment 18]
With 0.40g nanometer CuS powder (500nm), the 0.40g carbon black mixes the formation slurry at normal temperatures and pressures with the solution that the 0.20g Kynoar is dissolved in 2ml cyclopentanone gained, evenly is coated on the Copper Foil substrate the about 20 μ m of the film thickness of gained.All the other anode preparation steps are with embodiment 1.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 180m/g, and charging capacity is 90mAh/g.The 5th all discharge capacities are 50mAh/g.[embodiment 19]
Form identical anode by embodiment 1 described making.Be LiCoO to electrode accordingly 2, manufacture method is as follows: with 0.40gLiCoO 2Powder (5 μ m), the 0.40g carbon black mixes the formation slurry at normal temperatures and pressures with the solution that the 0.20g Kynoar is dissolved in 2ml cyclopentanone gained, evenly is coated on the aluminum substrates the about 20 μ m of gained film thickness.Other material of Experimental cell, structure, assembling and method of testing are all with embodiment 1.
Measurement result: first all charging capacitys are 347mAh/g, and discharge capacity is 292mAh/g.The 5th all charging capacitys are 263mAh/g.[embodiment 20]
With nanometer Cu 2S powder (60nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 309mAh/g, and discharge platform is at 1.6V; First all charging capacitys are 250mAh/g, and charging platform is at 1.8V.The 5th all discharge capacities are 195mAh/g.[embodiment 21]
Nanometer Fe S powder (60nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 98mAh/g, and discharge platform is at 1.4V; First all charging capacitys are 90mAh/g, and charging platform is respectively at 1.8V.The 5th all discharge capacities are 60mAh/g.[embodiment 22]
With nanometer Fe 2S powder (60nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 300mAh/g, and two discharge platforms are respectively at 1.6V and 1.5V; First all charging capacitys are 225mAh/g, and two charging platforms are respectively at 1.75V and 2.4V.The 5th all discharge capacities are 180mAh/g.[embodiment 23]
With nanometer Fe 3S 8Powder (110nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
First all discharge capacities are 450mAh/g, and discharge platform is at 1.5V; First all charging capacitys are 322mAh/g, and charging platform is at 2.3V.The 5th all discharge capacities are 267mAh/g.[embodiment 24]
With nanometer Li 2FeS 2Powder (90nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all charging capacitys are 280mAh/g, and two charging platforms are respectively at 2.0V and 2.5V; First all discharge capacities are 240mAh/g, and two discharge platforms are respectively at 2.4V and 2.0V.The 5th all charging capacitys are 210mAh/g.[embodiment 25]
With nanometer Sb 2S 3Powder (95nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 175mAh/g, and discharge platform is at 1.2V; First all charging capacitys are 130mAh/g, charging platform 2.0V.The 5th all discharge capacities are 60mAh/g.[embodiment 26]
With nano Co S 2Powder (80nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 220mAh/g, and discharge platform is at 1.7V; First all charging capacitys are 186mAh/g, and charging platform is at 2.1V.The 5th all discharge capacities are 135mAh/g.[embodiment 27]
With nano Co 2S 7Powder (80nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 520mAh/g, and discharge platform is at 1.9V; First all charging capacitys are 400mAh/g, and charging platform is at 2.5V.The 5th all discharge capacities are 230mAh/g.[embodiment 28]
With nanometer Ni 2S 7Powder (80nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 480mAh/g, and discharge platform is at 1.8V; First all charging capacitys are 390mAh/g, and charging platform is at 2.2V.The 5th all discharge capacities are 260mAh/g.[embodiment 29]
With nanometer V 2S 5Powder (60nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 140mAh/g, and discharge platform is at 1.93V; First all charging capacitys are 60mAh/g, and charging platform is at 2.5V.The 5th all discharge capacities are 40mAh/g.[embodiment 30]
With nanometer LiCrS 2Powder (60nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all charging capacitys are 140mAh/g, and charging platform is at 2.85V; First all discharge capacities are 120mAh/g, and discharge platform is respectively at 2.3V.The 5th all charging capacitys are 60mAh/g.[embodiment 31]
With nanometer ZrS 2Powder (150nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 80mAh/g, and discharge platform is at 1.85V: first all charging capacitys are 65mAh/g, and charging platform is at 2.15V.The 5th all discharge capacities are 40mAh/g.[embodiment 32]
With nanometer Cr 0.5V 0.5S 2Powder (100nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 95mAh/g, and discharge platform is at 2.2V; First all charging capacitys are 80mAh/g, and charging platform is at 2.35V.The 5th all discharge capacities are 65mAh/g.[embodiment 33]
With nanometer LiCr 0.5V 0.5S 2Powder (100nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all charging capacitys are 84mAh/g, and charging platform is at 2.4V; First all discharge capacities are 72mAh/g, and discharge platform is respectively at 2.2V.The 5th all charging capacitys are 58mAh/g.[embodiment 34]
Nano-tube/CdS powder (80nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 310mAh/g, and discharge platform is at 1.95V; First all charging capacitys are 230mAh/g, and charging platform is at 2.5V.The 5th all discharge capacities are 120mAh/g.[embodiment 35]
Nano PbS powder (80nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 205mAh/g, discharge platform 1.9,1.2V; First all charging capacitys are 150mAh/g, charging platform 2.0,2.4V.The 5th all discharge capacities are 82mAh/g.[embodiment 36]
With nanometer SiS 2Powder (80nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 217mAh/g, and discharge platform is at 2.26V; First all charging capacitys are 168mAh/g, and charging platform is at 2.8V.The 5th all discharge capacities are 95mAh/g.[embodiment 37]
With nanometer MnS 2Powder (55nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 86mAh/g, and discharge platform is at 1.2V; First all charging capacitys are 60mAh/g, and charging platform is at 2.3V.The 5th all discharge capacities are 42mAh/g.[embodiment 38]
With nanometer SnS 2Powder (120nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 66mAh/g, average discharge volt 1.6V; First all charging capacitys are 50mAh/g, average charging tension 2.3V.The 5th all discharge capacities are 27mAh/g.[embodiment 39]
With nanometer Ag 2S powder (80nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 205mAh/g, and discharge platform is at 1.38V; First all charging capacitys are 150mAh/g, and charging platform is at 2.1V.The 5th all discharge capacities are 80mAh/g.[embodiment 40]
Nanometer ZnS powder (70nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 153mAh/g, and discharge platform is at 1.45V; First all charging capacitys are 120mAh/g, and charging platform is at 2.05V.The 5th all discharge capacities are 87mAh/g.[embodiment 41]
With nanometer NbS 3Powder (90nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 160mAh/g, and discharge platform is at 1.8V; First all charging capacitys are 87mAh/g, and charging platform is at 2.4V.The 5th all discharge capacities are 80mAh/g.[embodiment 42]
With nanometer NbS 2Powder (90nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 90mAh/g, and discharge platform is at 2.0V; First all charging capacitys are 60mAh/g, and charging platform is at 2.4V.The 5th all discharge capacities are 50mAh/g.[embodiment 43]
With nanometer Bi 2S 3Powder (40nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 160mAh/g, and discharge platform is at 1.2V; First all charging capacitys are 125mAh/g, and charging platform is at 2.15V.The 5th all discharge capacities are 85mAh/g.[embodiment 44]
With nanometer TiS 3Powder (150nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 540mAh/g, and discharge platform is at 2.1V, 1.8V; First all charging capacitys are 150mAh/g, and charging platform is at 2.4V.The 5th all discharge capacities are 130mAh/g.[embodiment 45]
With nanometer MoS 3Powder (80nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 3.5V, be limited to outside the 1.5V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 240mAh/g, and discharge platform is at 2.5V; First all charging capacitys are 196mAh/g, and charging platform is at 3.3V.The 5th all discharge capacities are 127mAh/g.[embodiment 46]
With nanometer MoS 2Powder (80nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 122mAh/g, and discharge platform is at 1.8V; First all charging capacitys are 100mAh/g, and charging platform is at 2.2V.The 5th all discharge capacities are 70mAh/g.
[embodiment 47]
With nanometer VS 2Powder (80nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 137mAh/g, average discharge volt 2.1V; First all charging capacitys are 114mAh/g, average charging tension 2.5V.The 5th all discharge capacities are 98mAh/g.[embodiment 48]
Nanometer S powder (100nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 540mAh/g, and discharge platform is at 2.0V; First all charging capacitys are 350mAh/g, and charging platform is at 2.4V.The 5th all discharge capacities are 230mAh/g.
[embodiment 49]
With nanometer CuCo 2S 4Powder (130nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 167mAh/g, and discharge platform is at 1.5V; First all charging capacitys are 156mAh/g, and charging platform is at 2.1V.The 5th all discharge capacities are 121mAh/g.[embodiment 50]
With nanometer CuNi 2S 4Powder (130nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 135mAh/g, and discharge platform is at 1.4V; First all charging capacitys are 116mAh/g, and charging platform is at 2.1V.The 5th all discharge capacities are 93mAh/g.[embodiment 51]
With nanometer CuFeS 4Powder (140nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 110mAh/g, and discharge platform is at 1.3V; First all charging capacitys are 94mAh/g, and charging platform is at 2.0V.The 5th all discharge capacities are 80mAh/g.[embodiment 52]
Nanometer LiBr powder (80nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 4.2V, be limited to outside the 2.5V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all charging capacitys are 208mAh/g, and charging platform is at 4.1V; First all capacity are 167mAh/g, and discharge platform is at 3.5V.The 5th all charging capacitys are 127mAh/g.[embodiment 53]
With nanometer CuBr 2Powder (85nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 4.2V, be limited to outside the 2.5V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 166mAh/g, and discharge platform is at 3.4V; First all charging capacitys are 137mAh/g, and charging platform is at 4.15V.The 5th all discharge capacities are 104mAh/g.[embodiment 54]
Nanometer Ag Br powder (85nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 4.2V, be limited to outside the 2.5V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 151mAh/g, and discharge platform is at 3.35V; First all charging capacitys are 116mAh/g, and charging platform is at 4.1V.The 5th all discharge capacities are 89mAh/g.[embodiment 55]
With nanometer PbBr 2Powder (85nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 4.2V, be limited to outside the 2.5V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 126mAh/g, and discharge platform is at 3.2V; First all charging capacitys are 105mAh/g, and charging platform is at 4.1V.The 5th all discharge capacities are 81mAh/g.[embodiment 56]
With nanometer Cul 2Powder (70nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 3.5V, be limited to outside the 1.5V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 110mAh/g, and discharge platform is at 1.95V; First all charging capacitys are 99mAh/g, and charging platform is at 2.8V.The 5th all discharge capacities are 74mAh/g.[embodiment 57]
Nanometer Ag I powder (30nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 3.5V, be limited to outside the 1.5V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 90mAh/g, and discharge platform is at 2.0V; First all charging capacitys are 78mAh/g, and charging platform is at 2.8V.The 5th all discharge capacities are 62mAh/g.[embodiment 58]
Nanometer PbI powder (70nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 3.5V, be limited to outside the 1.5V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 70mAh/g, and discharge platform is at 1.8V; First all charging capacitys are 60mAh/g, and charging platform is at 2.8V.The 5th all discharge capacities are 47mAh/g.[embodiment 59]
With nanometer PbI 2Powder (80nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 3.5V, be limited to outside the 1.5V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 106mAh/g, and discharge platform is at 1.9V; First all charging capacitys are 84mAh/g, and charging platform is at 3.0V.The 5th all discharge capacities are 60mAh/g.[embodiment 60]
Nanometer LiI powder (80nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 3.5V, be limited to outside the 1.5V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all charging capacitys are 160mAh/g, and charging platform is at 2.8V; First all discharge capacities are 140mAh/g, and discharge platform is at 2.4V.The 5th all charging capacitys are 124mAh/g.[embodiment 61]
With nanometer I 2Powder (100nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 3.5V, be limited to outside the 1.5V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 180mAh/g, and discharge platform is at 2.8V; First all charging capacitys are 160mAh/g, and charging platform is at 3.2V.The 5th all discharge capacities are 1.50mAh/g.[embodiment 62]
With nanometer Li 2.5Co 0.4N powder (190nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 1.5V, be limited to outside the 0.0V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 450mAh/g, average discharge volt 0.3V; First all charging capacitys are 400mAh/g, average charging tension 1.0V.The 5th all discharge capacities are 370mAh/g.[embodiment 63]
With nanometer Li 2.6Cu 0.4N powder (190nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 1.5V, be limited to outside the 0.0V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 600mAh/g, average discharge volt 0.4V; First all charging capacitys are 500mAh/g, average charging tension 1.1V.The 5th all discharge capacities are 410mAh/g.[embodiment 64]
With nanometer Li 2.6Ni 0.4N powder (190nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 1.5V, be limited to outside the 0.0V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 180mAh/g, average discharge volt 0.35V; First all charging capacitys are 150mAh/g, average charging tension 1.0V.The 5th all discharge capacities are 104mAh/g.[embodiment 65]
With nanometer Li 3FeN 2Powder (190nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 1.5V, be limited to outside the 0.0V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 120mAh/g, average discharge volt 0.5V; First all charging capacitys are 98mAh/g, average charging tension 1.0V.The 5th all discharge capacities are 70mAh/g.[embodiment 66]
With nanometer Li 7MnN 4Powder (200nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 1.5V, be limited to outside the 0.0V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 210mAh/g, average discharge volt 0.6V; First all charging capacitys are 175mAh/g, average charging tension 1.1V.The 5th all discharge capacities are 121mAh/g.[embodiment 67]
With nanometer LiV 3O 8Powder (80nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 3.5V, be limited to outside the 1.5V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 200mAh/g, and discharge platform is at 2.6V; First all charging capacitys are 180mAh/g, and charging platform is at 3.0V.The 5th all discharge capacities are 159mAh/g.[embodiment 68]
With nanometer V 2O 5Powder (80nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 4.0V, be limited to outside the 2.0V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 125mAh/g, average discharge volt 3.2V; First all charging capacitys are 110mAh/g, and charging platform is at 3.5V.The 5th all discharge capacities are 100mAh/g.[embodiment 69]
With nanometer V 6O 13Powder (80nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 180mAh/g, average discharge volt 2.5V; First all charging capacitys are 147mAh/g, and charging platform is at 2.8V.The 5th all discharge capacities are 110mAh/g.[embodiment 70]
With nanometer LiVO 2Powder (80nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 4.0V, be limited to outside the 2.0V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all charging capacitys are 120mAh/g, average charging tension 3.3V; First all charging capacitys are 64mAh/g, and average discharge volt is at 3.0V.The 5th all charging capacitys are 60mAh/g.[embodiment 71]
With nanometer Bi 2O 3Powder (280nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 130mAh/g, average discharge volt 1.49V; First all charging capacitys are 60mAh/g, average charging tension 2.1V.The 5th all discharge capacities are 30mAh/g.[embodiment 72]
With nanometer LiMnO 2Powder (500nm) is made electrode by embodiment 1 described anode preparation step.Removing the charging cut-ff voltage is 4.2V, and discharge cut-off voltage is outside the 2.0V, other material of Experimental cell, and structure, assembling and method of testing are with embodiment 1.
Measurement result: first all charging capacitys are 145mAh/g, and charging platform is at 4.0V; First all discharge capacities are 120mAh/g, and discharge platform is at 2.8V.The 5th all charging capacitys are 110mAh/g.[embodiment 73]
With nanometer Cr 3O 8Powder (80nm) is made electrode by embodiment 1 described anode preparation step.Removing the charging cut-ff voltage is 4.0V, and discharge cut-off voltage is outside the 2.0V, other material of Experimental cell, and structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 280mAh/g, and discharge platform is at 2.8V; First all charging capacitys are 260mAh/g, and charging platform is at 3.5V.The 5th all discharge capacities are 220mAh/g.[embodiment 74]
With nanometer Pb 3O 4Powder (50nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 180mAh/g, and discharge platform is at 1.5V; First all charging capacitys are 156mAh/g, and charging platform is at 2.4V.The 5th all discharge capacities are 132mAh/g.[embodiment 75]
With nanometer Bi 2Pb 2O 5Powder (90nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 106mAh/g, and two discharge platforms are respectively at 1.7V and 1.5V; First all charging capacitys are 90mAh/g, and two charging platforms are respectively at 1.75V and 2.4V.The 5th all discharge capacities are 75mAh/g.[embodiment 76]
With nanometer Fe 2O 3Powder (60nm) is made electrode by embodiment 1 described anode preparation step.Removing the charging cut-ff voltage is 2.5V, and discharge cut-off voltage is outside the 0.5V, other material of Experimental cell, and structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 430mAh/g, and discharge platform is at 1.2V; First all charging capacitys are 266mAh/g, and charging platform is at 1.8V.The 5th all discharge capacities are 226mAh/g.[embodiment 77]
With nanometer WO 2Powder (80nm) is made electrode by embodiment 1 described anode preparation step.Removing the charging cut-ff voltage is 1.0V, and discharge cut-off voltage is outside the 0.0V, other material of Experimental cell, and structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 124mAh/g, discharge platform 0.7,0.5V; First all charging capacitys are 90mAh/g, charging platform 0.7,0.9V.The 5th all discharge capacities are 85mAh/g.[embodiment 78]
Nanometer CuO powder (80nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 160mAh/g, and discharge platform is at 1.35V; First all charging capacitys are 116mAh/g, and charging platform is at 2.5V.The 5th all discharge capacities are 74mAh/g.[embodiment 79]
With nanometer LiCuO 2Powder (85nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 4.0V, be limited to outside the 1.5V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 180mAh/g, and discharge platform is at 2.1V; First all charging capacitys are 170mAh/g, and charging platform is at 3.5V.The 5th all discharge capacities are 155mAh/g.[embodiment 80]
With nanometer LiNiO 2Powder (500nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 4.2V, be limited to outside the 2.5V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all charging capacitys are 200mAh/g, and charging platform is at 3.8V; First all discharge capacities are 176mAh/g, and discharge platform is at 3.7V.The 5th all charging capacitys are 160mAh/g.[embodiment 81]
With nanometer MoO 2Powder (85nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 105mAh/g, and discharge platform is at 2.95V; First all charging capacitys are 96mAh/g, and charging platform is at 3.1V.The 5th all discharge capacities are 80mAh/g.[embodiment 82]
With nanometer LiCoO 2Powder (500nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 4.2V, be limited to outside the 3.0V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all charging capacitys are 153mAh/g, and charging platform is at 4.05V; First all discharge capacities are 145mAh/g, and discharge platform is at 3.9V.The 5th all charging capacitys are 138mAh/g.[embodiment 83]
With nanometer Li 6Fe 2O 3Powder (180nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all charging capacitys are 84mAh/g, and charging platform is at 2.4V; First all discharge capacities are 76mAh/g, and discharge platform is at 1.4V.The 5th all charging capacitys are 65mAh/g.[embodiment 84]
Nanometer Fe OCl powder (80nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 4.0V, be limited to outside the 1.5V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 130mAh/g, and discharge platform is at 3.2V; First all charging capacitys are 115mAh/g, and charging platform is 3.45.The 5th all discharge capacities are 92mAh/g.[embodiment 85]
Nanometer CrOCl powder (60nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 146mAh/g, and discharge platform is at 2.1V; First all charging capacitys are 124mAh/g, and charging platform is at 2.7V.The 5th all discharge capacities are 108mAh/g.[embodiment 86]
Nanometer VOCl powder (60nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 109mAh/g, and discharge platform is at 2.1V; First all charging capacitys are 98mAh/g, and charging platform is at 2.8V.The 5th all discharge capacities are 80mAh/g.[embodiment 87]
Nanometer CrOBr powder (60nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
Measurement result: first all discharge capacities are 93mAh/g, and discharge platform is at 2.4V; First all charging capacitys are 81mAh/g, and charging platform is at 2.9V.The 5th all discharge capacities are 72mAh/g.[embodiment 88]
Nanometer Se powder (110nm) is made electrode by embodiment 1 described anode preparation step.Remove on the charging voltage and be limited to 3.5V, be limited to outside the 1.5V under the discharge voltage, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
First all discharge capacities are 110mAh/g, and discharge platform is at 2.1V; First all charging capacitys are 90mAh/g, and charging platform is at 2.3V.The 5th all discharge capacities are 68mAh/g.[embodiment 89]
With nanometer NbSe 4Powder (140nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
First all discharge capacities are 145mAh/g, and discharge platform is at 1.8V; First all charging capacitys are 105mAh/g, and charging platform is at 2.8V.The 5th all discharge capacities are 92mAh/g.[embodiment 90]
With nanometer NbSe 2Powder (140nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
First all discharge capacities are 103mAh/g, and discharge platform is at 1.6V; First all charging capacitys are 86mAh/g, and charging platform is at 2.8V.The 5th all discharge capacities are 72mAh/g.[embodiment 91]
With nanometer NbSe 3Powder (140nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
First all discharge capacities are 131mAh/g, and discharge platform is at 1.6V; First all charging capacitys are 92mAh/g, and charging platform is at 2.1V.The 5th all discharge capacities are 76mAh/g.[embodiment 92]
With nanometer TiSe 2Powder (80nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
First all discharge capacities are 115mAh/g, discharge platform 2.05,1.7V; First all charging capacitys are 110mAh/g, charging platform 1.8,2.2V.The 5th all discharge capacities are 95mAh/g.[embodiment 93]
With nanometer VSe 2Powder (160nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
First all discharge capacities are 124mAh/g, and discharge platform is at 1.9V; First all charging capacitys are 116mAh/g, and charging platform is at 2.5V.The 5th all discharge capacities are 103mAh/g.[embodiment 94]
With nanometer ZrSe 2Powder (90nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
First all discharge capacities are 123mAh/g, and discharge platform is at 1.6V; First all charging capacitys are 96mAh/g, and charging platform is at 2.8V.The 5th all discharge capacities are 62mAh/g.[embodiment 95]
With nanometer LiZrSe 2Powder (80nm) is made electrode by embodiment 1 described anode preparation step.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
First all charging capacitys are 231mAh/g, and charging platform is at 2.4V; First all discharge capacities are 186mAh/g, and discharge platform is at 1.7V.The 5th all charging capacitys are 152mAh/g.[embodiment 96]
With nanometer IF 3Powder (210nm) carbon black mixes the formation slurry at normal temperatures and pressures with the cyclopentanone solution of Kynoar, evenly is coated on the Copper Foil substrate as collector the about 20 μ m of the film thickness of gained.After the film vacuumize at normal temperatures that obtains, at 20Kg/cm 2Under compress, continued vacuumize at normal temperatures 12 hours.Make electrode by embodiment 1 described anode preparation step again.Remove on the charging voltage and be limited to 4.2V, be limited to 1.0V under the discharge voltage, charging and discharging currents density is 1mA/cm 2Outside, other material of Experimental cell, structure, assembling and method of testing are with embodiment 1.
First all discharge capacities are 180mAh/g, and discharge platform is at 3.5V; The first charging Zhou Rongliang is 60mAh/g, and charging platform is at 3.1V.The 5th all discharge capacities are 42mAh/g.[embodiment 97]
Nanometer ICl powder (210nm) is made electrode by embodiment 96 described anode preparation steps.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 96.
First all discharge capacities are 143mAh/g, and discharge platform is at 3.3V; The first charging Zhou Rongliang is 55mAh/g, and charging platform is at 3.15V.The 5th all discharge capacities are 36mAh/g.[embodiment 98]
Nanometer IBr powder (240nm) is made electrode by embodiment 96 described anode preparation steps.Other material of Experimental cell, structure, assembling and method of testing are with embodiment 96.
First all discharge capacities are 117mAh/g, and discharge platform is at 3.2V; The first charging Zhou Rongliang is 58mAh/g, and charging platform is at 3.1V.The 5th all discharge capacities are 40mAh/g.

Claims (12)

1. a serondary lithium battery comprises anode, negative electrode, organic electrolyte solution or solid electrolyte, its spy
Levy and be that at least one side of described anode and negative electrode is contained disperse phase nanometer combined electrode material, disperse
The phase nanometer combined electrode material comprises two ones of the electrode active material that can store, discharge lithium and disperse means
Divide; The granularity of electrode active material wherein is between 500nm～1nm, and it is at the disperse phase composite wood
Shared percentage by weight is 95% to 30% in the material, and surplus is disperse means.
2. by the described serondary lithium battery of claim 1, have at least a kind of in the wherein said electrode active material
Be (A) nanometer sulphur, nanometer sulfide, nanometer polysulfide and the nanometer sulfide that contains lithium; (B) receive
Rice bromide and contain the nanometer bromide of lithium; (C) nanometer iodine, nanometer iodide and contain the nanometer iodine of lithium
Change thing; (D) nano nitride and contain the nano nitride of lithium; (E) nano-oxide and contain receiving of lithium
The rice oxide; (F) nanometer selenium, nanometer selenides and contain the nanometer selenides of lithium; (G) nanometer halogen
Between compound.
3. by claim 1,2 described serondary lithium batteries, wherein said electrode active material (A) nanometer
Sulphur, nanometer sulfide, nanometer polysulfide and contain the nanometer sulfide of lithium, are received its nanometer sulfide
Rice polysulfide and the nanometer sulfide feature that contains lithium are: the compound of metallic element and sulphur formation, gold
Belong to element comprise Bi, Si, Sb, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pb, Ag,
Nb、Mo、Sn、W、Cd、Zr。
4. by claim 1,2 described serondary lithium batteries, wherein said electrode active material (B) nanometer
Bromide and contain the nanometer bromide of lithium is characterized in that: the compound that metallic element and bromine form, gold
Belong to element and comprise Li, Cu, Ag, Pb.
5. by claim 1,2 described serondary lithium batteries, wherein said electrode active material (C) nanometer
Iodine, nanometer iodide and contain the nanometer iodide of lithium, its nanometer iodide and contain the nanometer iodide of lithium
Feature is: the compound that metallic element and iodine form, metallic element comprises Li, Cu, Ag, Pb.
6. by claim 1,2 described serondary lithium batteries, wherein said electrode active material (D) nanometer
Nitride and contain the nano nitride of lithium is characterized in that: the compound that metallic element and nitrogen form, gold
Belong to element and comprise Mn, Fe, Co, Ni, Cu.
7. by claim 1,2 described serondary lithium batteries, wherein said electrode active material (E) nanometer
Oxide and contain the nano-oxide of lithium is characterized in that: the compound that metallic element and oxygen form, gold
Belong to element and comprise Ti, V, Fe, Co, Cu, Pb, Bi, Cr, W, Mo, Mn, Ni.
8. by claim 1,2 described serondary lithium batteries, wherein said electrode active material (F) nanometer
Selenium, nanometer selenides and contain the nanometer selenides of lithium, its nanometer selenides and contain the nanometer selenides of lithium
Feature is: the compound that metallic element and selenium form comprises Ti, V, Pb, Nb, Zr.
9. by claim 1,2 described serondary lithium batteries, wherein said electrode active material (G) nanometer
Interhalogen compounds is IF 3, ICl, IBr.
10. by the described serondary lithium battery of claim 1, it is characterized in that: described disperse means comprise the conduction interpolation
Agent and adhesive, wherein conductive additive shared percentage by weight in the disperse phase nano composite material
Be 0% to 60%, the binder constitutes percentage by weight is 2%-30%.
11. by claim 1,10 described serondary lithium batteries, it is characterized in that: described conductive additive comprises
Cu, Al, Ni, Fe, Ag powder, acetylene black, carbon black, graphite powder, carbon fiber, mesocarbon bead
Or polyaniline, conducting polymers such as polypyrrole.Its granularity is 1nm～20um.
12. by claim 1,10 described serondary lithium batteries, it is characterized in that: described adhesive comprises poly-four
PVF, Kynoar, polyacrylonitrile, poly(ethylene oxide), ethylene-propylene rubber.
CN99100282A 1999-01-28 1999-01-28 Secondary lithium battery Pending CN1262533A (en)

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Cited By (16)

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CN100355123C (en) * 2002-09-23 2007-12-12 三星Sdi株式会社 Positive active material of a lithium-sulfur battery and method of fabricating same
CN100367547C (en) * 2002-06-05 2008-02-06 中国人民解放军63971部队 Carbon heterocyclic ring or replacement carboatomic ring polysulfide for lithium battery anode material
CN100367562C (en) * 2006-01-05 2008-02-06 复旦大学 Thin film lithium ion cell using silver selenide film as anode material and its preparing method
CN100384000C (en) * 2006-05-11 2008-04-23 复旦大学 Film lithium ion cell with zinc selenide film as anode and method for preparing same
CN101847740A (en) * 2009-03-23 2010-09-29 三洋电机株式会社 Rechargeable nonaqueous electrolytic battery
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CN107665986A (en) * 2016-07-29 2018-02-06 横店集团东磁股份有限公司 A kind of iodide battery anode slice and preparation method thereof
CN107665975A (en) * 2016-07-29 2018-02-06 横店集团东磁股份有限公司 A kind of interhalogen compounds battery anode slice and preparation method thereof
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CN107834074A (en) * 2017-11-02 2018-03-23 四川华昆能源有限责任公司 A kind of preparation method of lithium-sulfur cell solid state cathode additive and the sulphur negative electrode containing the additive
CN108565485A (en) * 2018-04-04 2018-09-21 东华大学 A kind of sulphur based on liquid electrode-bromine rechargeable battery and its application
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CN100367547C (en) * 2002-06-05 2008-02-06 中国人民解放军63971部队 Carbon heterocyclic ring or replacement carboatomic ring polysulfide for lithium battery anode material
CN100355123C (en) * 2002-09-23 2007-12-12 三星Sdi株式会社 Positive active material of a lithium-sulfur battery and method of fabricating same
CN100367562C (en) * 2006-01-05 2008-02-06 复旦大学 Thin film lithium ion cell using silver selenide film as anode material and its preparing method
CN100384000C (en) * 2006-05-11 2008-04-23 复旦大学 Film lithium ion cell with zinc selenide film as anode and method for preparing same
CN101916859A (en) * 2009-03-12 2010-12-15 巴莱诺斯清洁能源控股公司 Nitride and carbide anode materials
CN101847740A (en) * 2009-03-23 2010-09-29 三洋电机株式会社 Rechargeable nonaqueous electrolytic battery
CN103700820A (en) * 2014-01-07 2014-04-02 中国科学院化学研究所 Lithium ion selenium battery with long service life
CN107665992A (en) * 2016-07-29 2018-02-06 横店集团东磁股份有限公司 A kind of polydentate compound battery anode slice and preparation method thereof
CN107665986A (en) * 2016-07-29 2018-02-06 横店集团东磁股份有限公司 A kind of iodide battery anode slice and preparation method thereof
CN107665975A (en) * 2016-07-29 2018-02-06 横店集团东磁股份有限公司 A kind of interhalogen compounds battery anode slice and preparation method thereof
CN107665992B (en) * 2016-07-29 2020-08-25 横店集团东磁股份有限公司 Positive plate of polyhalogen compound battery and preparation method thereof
CN107665986B (en) * 2016-07-29 2020-10-02 横店集团东磁股份有限公司 Iodide battery positive plate and preparation method thereof
CN107068989A (en) * 2016-12-23 2017-08-18 浙江大学 A kind of positive electrode for lithium-iodine battery
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CN107785564A (en) * 2017-10-18 2018-03-09 武汉理工大学 VTi2.6O7.7Nano particle, preparation and application
CN107834074A (en) * 2017-11-02 2018-03-23 四川华昆能源有限责任公司 A kind of preparation method of lithium-sulfur cell solid state cathode additive and the sulphur negative electrode containing the additive
CN108565485A (en) * 2018-04-04 2018-09-21 东华大学 A kind of sulphur based on liquid electrode-bromine rechargeable battery and its application
CN108565485B (en) * 2018-04-04 2021-06-11 东华大学 Sulfur-bromine rechargeable battery based on liquid electrode and application thereof
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