CN103915621B - Novel negative electrode active material and respective negative and respective battery - Google Patents
Novel negative electrode active material and respective negative and respective battery Download PDFInfo
- Publication number
- CN103915621B CN103915621B CN201310006822.6A CN201310006822A CN103915621B CN 103915621 B CN103915621 B CN 103915621B CN 201310006822 A CN201310006822 A CN 201310006822A CN 103915621 B CN103915621 B CN 103915621B
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- battery
- active material
- electrode active
- negative electrode
- negative
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- 239000000126 substance Substances 0.000 claims abstract description 12
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- 239000002184 metal Substances 0.000 claims description 16
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- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 9
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- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910001884 aluminium oxide Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000001351 cycling Effects 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002587 enol group Chemical group 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- MCUJFJGJUYOITH-UHFFFAOYSA-N lithium(1-);nickel;oxygen(2-) Chemical compound [Li-].[O-2].[O-2].[O-2].[O-2].[O-2].[Ni].[Ni].[Ni].[Ni] MCUJFJGJUYOITH-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000479 mixture part Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N n-methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
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- 229920000098 polyolefin Polymers 0.000 description 1
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- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- BFASWJXWTSCDRR-UHFFFAOYSA-M prop-2-enyl carbonate Chemical compound [O-]C(=O)OC[C]=C BFASWJXWTSCDRR-UHFFFAOYSA-M 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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Abstract
It is an object of the invention to provide a kind of cheap and new type lithium ion battery negative material of high power capacity, and the nonaqueous electrolytic solution secondary battery with long-life, high power capacity using this negative pole is provided.This negative pole at least contains a kind of sulfur simple substance as negative electrode active material or sulphur compound and a kind of transition metal powders；This nonaqueous electrolytic solution secondary battery possesses positive pole, above-mentioned negative pole, barrier film and nonaqueous electrolytic solution.
Description
Technical field
The present invention relates to electrochemical energy source domain, particularly relate to the negative electrode active material of a kind of lithium ion battery, and contain
The respective negative of this negative electrode active material, and use the high performance lithium ion battery of this negative pole.
Background technology
Lithium rechargeable battery is the electrical energy storage device of a kind of high efficiency, high-energy-density, has been widely used in
Small movable electronic equipment.As other battery systems, lithium ion battery mainly has positive electrode, negative material, barrier film
Critical material big with electrolyte four is constituted, and the character of material and the performance of lithium ion battery have very important relation.At present
The widely used positive electrode of lithium ion battery is mainly lithium ion can reversibly embed-the transiting metal oxidation of deintercalate lithium ions
Thing, as with cobalt acid lithium (LiCoO2), ternary material (LiNi1/3Co1/3Mn1/3O2) etc. for the layered metal oxide of representative, with manganese
Acid lithium (LiMn2O4) be the spinel-type metal-oxide of representative, with LiFePO4 (LiFePO4) be representative olivine-type gold
Belong to oxide etc.；Negative material is that lithium ion can reversibly embed-the compound of deintercalation, such as lamellar graphite.These high-performance materials
The application of material, determines lithium ion battery today as small-sized portable type communication electronic equipment (such as mobile phone, hand-held computer etc.)
Power supply can not shake status.But it is along with the further development (such as electric automobile requirement in terms of power source) of society, existing
Some lithium-ion battery systems all need to carry at price, safety, specific capacity and power-performance, the raw-material aspect such as plentiful
High.Material and the corresponding lithium ion cell electrode of exploitation higher performance are important.
Elemental sulfur, as the positive electrode of battery, have high energy density, abundant natural resources, cheap and
The multiple advantage such as environmental friendliness.Sulfur as theoretical specific capacity 1675mAh/g of the positive electrode of battery it is considered to be very good
Anode material for lithium ion battery of future generation；If negative pole uses lithium metal (theoretical specific capacity 3860mAh/g), the lithium of formation
Sulfur rechargeable battery theoretical energy density can reach 2680Wh/Kg, is preferable high-energy density secondary battery.But at lithium sulfur electricity
Chi Zhong, sulfur and discharging product thereof are all electronics and ion insulator, and many lithium sulfides that reduction process produces are soluble in organic electrolysis
In liquid solvent, these cause, and Li-S secondary cell high rate performance is poor, active material utilization is low, capacity attenuation is rapid, thus limits
Make its development (seeing documents and materials: 1) P.G.Bruce, S.A.Freunberger, L.J.Hardwick, and J-
M.Tarascon,Nat.Mater.,2012,11,19；2) A.Manthiram, Y.-Z.Fu, and Y.-S.Su.,
Acc.Chem.Res.,ASAP；3) X.Ji, K.T.Lee, and L.F.Nazar, Nat.Mater., 2009,8,500 etc.).
For improving the cycle characteristics of lithium-sulfur cell, it is proposed that various solutions, such as U.S. Patent No. 7250233
Number and No. 7078124, though to battery performance, some improves these methods, but practical application effect is the most obvious.The present invention
Main inventive people once by vitochemical method, sulfur was fixed on (Japanese Patent No. on the C-C skeleton of organic molecule
No. 3871306, Japanese Patent No. 4208451, Japanese Patent No. 4297673, Japanese Patent No. 4674883, the U.S. is special
Profit the 6709787th) greatly suppress the problems of dissolution of sulfur, but relative to elemental sulfur, the manufacturing cost of this material is higher, battery
Capacity has lowered.
Summary of the invention
It is an object of the present invention to provide a kind of new type lithium ion battery negative electrode active material, this negative electrode active material has
There are good electric conductivity, high utilization efficiency, excellent cycle performance.The present invention provide negative electrode active material, including to
Few a kind of sulfenyl material and at least one transition metal powders.This negative electrode active material in negative pole preparation process, and with
In the battery charging and discharging activation process that described negative pole is assembled into, with the reaction of sulfenyl material with transition metal powders.
Sulfenyl material of the present invention is selected from sulfur simple substance (S8)、Li2Sn(n >=1), organosulfur compound, inorganic sulphide
In one or more.From high power capacity and the angle of low price of negative pole, preferably sulfur simple substance (S8) and Li2Sn(n≥8)。
Sulfur content combination property when 10 ~ 80wt% in negative electrode active material composition is preferable.The lowest, as the negative pole material of battery
Material capacity is relatively low, and time the highest, the cycle characteristics of battery reduces.
Transition metal powders of the present invention, including selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr,
The elemental metals powder of a kind of element or several unit in Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Ta, W, Re, Os, Ir, Pt and Au
The alloyed metal powder of element, also includes described elemental metals powder or alloyed metal powder partial oxidation or the product of partial vulcanization
Thing.The wherein metal material such as the preferred copper of elemental metals powder, nickel, cobalt, molybdenum, titanium.The preferred micron level of particle diameters, more excellent
Select Nano grade.Described transition metal powders element sulphur chemical combination in lithium-sulfur cell charge and discharge process and in negative electrode active material
Generate electrical conductivity height, the compound of stable cycle performance, make element sulphur be fixed, improve the specific capacity of material.
It is a further object to provide a kind of new type lithium ion battery negative pole, negative pole of the present invention have with
Lower feature, its composition contains:
At least one sulfenyl material (sulfur simple substance or sulphur compound)；
At least one transition metal powders；
The binding agents such as appropriate conductive agent and appropriate polyvinylidene fluoride (PVDF)；And
Conductive current collector.
Negative pole of the present invention, can be prepared by following method: suitable in the negative electrode active material that the present invention provides
After adding the binding agent such as conductive agent and appropriate polyvinylidene fluoride (PVDF), molten with METHYLPYRROLIDONE (NMP) etc.
Agent is dissolved is dispersed into mixture constituent containing negative electrode active material (stick with paste, slurry etc.), and described mixture constituent is applied to aluminum
The one or two sides of the conductive current collector such as paper tinsel, then remove solvent, ultimately form the banding containing negative electrode active material mixture layer and shape
Body.But the manufacture method of negative pole is not limited to foregoing illustrative method.
Described conductive agent is selected from material with carbon element, such as carbon black conductive agent (acetylene black, Super P, Super S, 350G, carbon
Fiber (VGCF), CNT (CNTs), Ketjen black (KetjenblackEC300J, KetjenblackEC600JD, Carbon
ECP, Carbon ECP600JD) etc.), graphite agent (KS-6, KS-15, SFG-6, SFG-15 etc.) carbon nano rod and Graphene
A kind of conductive material in Deng or the mixture of different materials.
The acting as of binding agent in the present invention, is adhered to above-mentioned negative electrode active material on collector, and strengthens negative pole
Mechanical integrity, improve solid-solid interface and/or solid-liquid interface physical electrical contact, increase the electronics of whole negative pole and ion
Conductive performance.Can select the different binding agent such as water system, oil system, this binding agent is selected from polyvinylidene fluoride (PVDF), poly-second
Enol (PVA), polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC), TPO (PP, PE etc.), nitrile rubber
(NBR), one or more in the polymer such as butadiene-styrene rubber (SBR), polyacrylonitrile (PAN), polyvinyl alcohol (PVA).
As long as conductive current collector of the present invention has electric conductivity, it is not particularly limited, usually conductive metal material.
According to embodiment of the present invention, this collector is conductive metallic material or the alloy of several metal, as Al, Fe, Co, Ni, Cu,
A kind of element simple substance in Zn, Ag, Pt and Au or the alloy of several element.From the angle of price and processability be preferably used aluminum and
Copper current collector.
The lithium-sulfur cell that negative electrode active material provided by the present invention and respective negative obtain, compared with conventional lithium-sulfur cell
The key factor that performance is significantly improved is, metal collector and transition metal powders to a certain extent with negative electrode active
Element sulphur chemical combination in material, generates electrical conductivity height, the compound of stable cycle performance, makes element sulphur be fixed, improve
The utilization rate of element sulphur, and make prepared lithium-sulfur cell have the cycle performance of excellence.
It is a further object to provide a kind of battery using negative electrode active material noted earlier and respective negative.
The battery of the present invention in addition to using negative electrode active material noted earlier and respective negative, its also include in constituting positive pole, barrier film and
The required parts such as nonaqueous electrolytic solution.So the nonaqueous electrolytic solution secondary battery of the present invention, as long as having above-mentioned negative electrode active material
And respective negative, other elements are not particularly limited, can use and existing known non-aqueous electrolyte secondary
The element that battery is same.
The positive electrode that generally lithium ion battery uses can use in the present invention.The positive electrode active material that positive pole relates to
Matter, it is possible to use the compound of reversibly occlusion-releasing (embedding and deintercalation) lithium ion, uses Li for example, it is possible to enumeratexMO2Or
LiyM2O4Lithium-contained composite oxide that (in formula, M is transition metal, 0≤x≤1,0≤y≤2) represents, the oxidation of spinelle shape
Thing, the metal chalcogenide of layer structure, olivine structural etc..
As its object lesson, LiCoO can be enumerated2Deng lithium and cobalt oxides, LiMn2O4Deng lithium manganese oxide, LiNiO2Deng
Lithium nickel oxide, Li4/3Ti5/3O4Deng Li-Ti oxide, li-mn-ni compound oxide, lithium manganese nickel cobalt composite oxides；Have
LiMPO4Materials of olivine-type crystalline texture such as (M=Fe, Mn, Ni) etc..
Lithium-contained composite oxide especially with layer structure or spinelle shape structure is preferred, LiCoO2、
LiMn2O4、LiNiO2、LiNi1/2Mn1/2O2Deng for the li-mn-ni compound oxide of representative, LiNil/3Mn1/3Co1/3O2、
LiNi0.6Mn0.2Co0.2O2Deng for the lithium manganese nickel cobalt composite oxides of representative or LiNi1-x-y-zCoxAlyMgzO2(in formula, 0≤x≤
1,0≤y≤0.1,0≤z≤0.1,0≤1-x-y-z≤1) etc. lithium-contained composite oxide.It addition, it is above-mentioned containing lithium combined oxidation
A part for constitution element in thing, by the addition element of Ge, Ti, Zr, Mg, Al, Mo, Sn etc. replaced containing lithium combined oxidation
Things etc. also comprise wherein.
These positive active materials, both can be used alone a kind, it is possible to two or more is also used.Such as, by using layer simultaneously
The lithium-contained composite oxide of shape structure and the lithium-contained composite oxide of spinel structure, can seek to take into account high capacity and safety
The raising of property.
For constituting the positive pole of nonaqueous electrolytic solution secondary battery, such as, in above-mentioned positive active material, it is properly added charcoal
The conductive auxiliary agents such as black, acetylene black, or the binding agent such as Kynoar, poly(ethylene oxide) etc., prepare anode mixture, by it with aluminum
The current-collecting members such as paper tinsel use as after coating on the banding molded body of core.But, on the manufacture method of positive pole is not limited only to
Example.
In the nonaqueous electrolytic solution secondary battery that the present invention provides, do not make spy for the barrier film that positive pole and negative pole are separated yet
Do not limit, the various barrier films used in existing known nonaqueous electrolytic solution secondary battery can be used.
Owing to the effect of barrier film is to be separated by the both positive and negative polarity active substance of battery, it is to avoid any electron stream of positive and negative interpolar is direct
Pass through, it is to avoid battery short circuit；The ion out-of-date resistance of circulation is little as far as possible, so mostly selecting apertured polymeric film.Such as, adopt
With the polyolefin resin such as polyethylene, polypropylene, or the pore that the polyester resin such as polybutylene terephthalate (PBT) is formed
Barrier film is preferred.It addition, these pore barrier films (pore film) also can overlapping use.Above-mentioned polymer microporous film is through material
The thin film obtained after surface modification, the composite ceramics barrier film being coated on polyolefin such as ceramic powder (aluminium oxide, silicon oxide etc.)
Can also use.
The thickness of barrier film is not particularly limited yet, but considers safety and high capacity two aspect of battery, preferably
For 5-30 μm.It addition, the air permeability of barrier film (s/100mL) is not particularly limited yet, but preferably 10-1000(s/100mL), more excellent
Select 50-800(s/100mL), particularly preferably 90-700(s/100mL).
In the nonaqueous electrolytic solution secondary battery that the present invention provides, use nonaqueous solvent (organic solvent) as non-aqueous solution electrolysis
Liquid, wherein the nonaqueous solvent of high-k is preferred.Owing to sulfide (the particularly inductor of elemental sulfur) is at carbonic ester
The electrolyte of class is difficult to solvation, in the electrolyte that this kind solvent is constituted, is generally difficult to discharge and recharge, so many ethers R
(CH2CH2O) n-R'(n=1-6;R and R' is methyl or ethyl etc.) it is preferred, particularly dimethyl ether tetraethylene glycol (TEG) (TEGDME), second
Glycol dimethyl ether (DME), 1,3-dioxolane (DOL) etc. is it is furthermore preferred that these solvents are high to polysulfide solubility, stable
Property is good.
It addition, a small amount of interpolation of carbonate-containing class is feasible.Wherein, it is recommended to use dielectric constant is the ester of more than 30.
As the ester of such high-k, for example, it is possible to enumerate ethylene carbonate, Allyl carbonate, butylene, γ-fourth
Lactone, sulfur class ester (ethylene glycol sulfide etc.) etc..Wherein, preferably cyclic ester, ethylene carbonate, vinylene carbonate, carbonic acid third
The cyclic carbonates such as alkene ester, butylene are particularly preferred.In addition to above-mentioned solvent, dimethyl carbonate, carbonic acid can be used
Low viscous polarity linear carbonate that diethylester, Ethyl methyl carbonate etc. are representative, aliphatic branched chain type carbonats compound.
Cyclic carbonate (particularly ethylene carbonate) is particularly preferred with the mixed solvent of linear carbonate.
It addition, in addition to above-mentioned nonaqueous solvent, the chains such as chain-like alkyl esters, trimethyl phosphate such as methyl propionate can be used
Phosphotriester；The nitrile solvents such as 3-methoxypropionitrile；The branched chain type compound with ehter bond with dendrimer as representative
Deng nonaqueous solvent (organic solvent).
It addition, may be used without fluorine kind solvent.
As fluorine kind solvent, for example, it is possible to enumerate H (CF2)2OCH3、C4F9OCH3、H(CF2)2OCH2CH3、H(CF2)2OCH2CF3、H(CF2)2CH2O(CF2)2H etc. or CF3CHFCF2OCH3、CF3CHFCF2OCH2CH3(perfluor alkane etc. linear chain structure
Base) alkyl ether, i.e. 2-trifluoromethyl hexafluoro propyl methyl ether, 2-trifluoromethyl hexafluoro propyl group ether, 2-trifluoromethyl hexafluoro propyl group
Propyl ether, 3-trifluoromethyl octafluoro butyl methyl ether, 3-trifluoromethyl octafluoro butyl ether, 3-trifluoromethyl octafluoro butyl propyl ether, 4-
Trifluoromethyl ten fluorine amyl group methyl ether, 4-trifluoromethyl ten fluorine amyl group ether, 4-trifluoromethyl ten fluorine amyl group propyl ether, 5-trifluoromethyl
Ten difluoro hexyl methyl ethers, 5-trifluoromethyl ten difluoro hexyl ether, 5-trifluoromethyl ten difluoro hexyl propyl ether, 6-trifluoromethyl ten
Tetrafluoro heptyl methyl ether, 6-trifluoromethyl ten tetrafluoro heptyl ether, 6-trifluoromethyl ten tetrafluoro heptyl propyl ether, 7-trifluoromethyl 16
Fluorine octyl group methyl ether, 7-trifluoromethyl ten hexafluoro octyl group ether, 7-trifluoromethyl ten hexafluoro octyl group propyl ether etc..
It addition, (perfluoroalkyl) alkyl ether of above-mentioned different (perfluoroalkyl) alkyl ether and above-mentioned linear chain structure also can and be used.
As the electrolytic salt used in nonaqueous electrolytic solution, the preferably perchlorate of lithium, organic boron lithium salts, fluorochemical
Lithium salts, the lithium salts such as lithium imide salts.
As the example of such electrolytic salt, for example, it is possible to enumerate LiClO4、LiPF6、LiBF4、LiAsF6、LiSbF6、
LiCF3SO3、LiCF3CO2、LiC2F4(SO3)2, LiN(C2F5SO2)2, LiC(CF3SO2)3、LiCnF2n+1SO3(n≥2)、LiN
(RfOSO2)2(in formula, Rf is fluoroalkyl) etc..In these lithium salts, fluorine-containing organic lithium salt is particularly preferred.Fluorine-containing organolithium
Salt, owing to anionic property is big and easily separated one-tenth ion, soluble in nonaqueous electrolytic solution.
Electrolyte lithium salt concentration in nonaqueous electrolytic solution, such as, 0.3mol/L (mol/L) is above preferably, more
Preferably more than 0.7mol/L, preferably below 1.7mol/L, more preferably below 1.2mol/L.When the concentration of electrolyte lithium salt is too low
Time, ionic conduction is spent little, time too high, worries that failing to dissolve electrolytic salt completely separates out.
It addition, in nonaqueous electrolytic solution, it is also possible to add the various additives of the performance that can improve the battery using it, not
It is particularly limited.
Such as, use the nonaqueous electrolytic solution that with the addition of the compound that intramolecular has C=C unsaturated bond, sometimes can suppress
Use the reduction of its battery charging and discharging cycle characteristics.
There is the compound of C=C unsaturated bond as this intramolecular, for example, it is possible to enumerate C6H5C6H11(cyclohexylbenzene) etc.
Aromatic compound；H(CF2)4CH2OOCCH=CH2, F(CF2)8CH2CH2OOCCH=CH2Etc. the aliphatic compound being fluorinated；Contain
The aromatic compound etc. of fluorine.It addition, 1,3-third sultone, 1,2-PD sulfuric ester is the main compound with element sulphur
(such as, chain or cyclic sulfonic acid ester, chain or cyclic sulfates etc.), vinylene carbonate base ester, vinyl ethylene carbonate, carbon
Acid ethylene fluoride ester etc. can also use, the most highly effective.Particularly when negative electrode active material uses highly crystalline material, carbon
The combined effects such as acid ethenylidene ester, vinyl ethylene carbonate, carbonic acid ethylene fluoride ester are more preferable.Adding of these various additives
Dosage, is preferred to nonaqueous electrolytic solution total amount for example, 0.05-5wt%.
Further, above-mentioned vinylene carbonate, vinyl ethylene carbonate, carbonic acid ethylene fluoride ester, use containing these chemical combination
The battery of the nonaqueous electrolytic solution of thing, by charging, forms protecting film in negative terminal surface, suppresses by negative electrode active material and non-water power
Solve liquid and contact the reaction that causes, there is the effect of the decomposition etc. of nonaqueous electrolytic solution preventing from being caused by this reaction.
Additionally, the improvement of the hot properties in order to realize nonaqueous electrolytic solution secondary battery, also can add in nonaqueous electrolytic solution
Add anhydride.
Anhydride, the surface modifier as negative pole is relevant with at negative terminal surface formation composite membrane, has battery when making high temperature
The function that more improves such as storing property.It addition, by anhydride is added to nonaqueous electrolytic solution, owing to non-aqueous electricity can be made
Solve the moisture in liquid to reduce, it is possible to make the gas generating capacity in the battery of this nonaqueous electrolytic solution of employing reduce.
Add the anhydride to nonaqueous electrolytic solution, be not particularly limited, both can be that intramolecular has at least 1 acid anhydride structure
Compound, it is also possible to be the compound with multiple acid anhydride structure.
As the object lesson of anhydride, for example, it is possible to enumerate mellitic acid trianhydride, malonic anhydride, maleic anhydride, butyryl oxide.,
Propionic andydride, pulvinic acid acid anhydride, phthalone anhydride, phthalic anhydride, pyromellitic acid dianhydride, lactic anhydride, naphthalic anhydride, toluene anhydride,
Thiobenzoate acid anhydride, biphenyl anhydride, citraconic anhydride, diethylene glycol amide anhydride, acetic anhydride, succinic anhydrides, cinnamic anhydride, 1,3-propanedicarboxylic acid
Acid anhydride, glutaconic anhydride, valeric anhydride, itaconic anhydride, different butyric acid anhydride, isovaleric anhydride, benzoyl oxide etc., these can use a kind or 2
More than Zhong.It addition, the addition of the anhydride in nonaqueous electrolytic solution, nonaqueous electrolytic solution total amount is preferred for 0.05-1wt%.
The preparation method of the nonaqueous electrolytic solution secondary battery that the present invention provides, such as, between aforementioned positive electrode and negative pole, folder
Live after aforementioned barrier film in addition overlapping, make electrode layer laminate, wound after making electrode coiling body, be filled in packaging body,
Positive and negative electrode is attached by lead body (lead wire) etc. with the positive and negative electrode terminal of packaging body, more aforementioned nonaqueous electrolytic solution is noted
After entering in packaging body, sealed package and make.
As the packaging body of battery, the packaging bodies such as square, cylindrical shape that metal makes can be used, or by metal (aluminum
Deng) laminated film formed layered product packaging body etc..
Further, the manufacture method of nonaqueous electrolytic solution secondary battery and the structure of battery, it is not particularly limited, in packaging body
After positive pole, negative pole, barrier film and nonaqueous electrolytic solution are set, before battery fully seals, the open formation process being charged is set
It is preferred.
So, in the charging initial stage produces gas or battery, the moisture of residual is removable to outside battery.
The method removing electricity pool gas after carrying out above-mentioned open formation process, is not particularly limited, can use nature
Remove or any one of vacuum removing.It addition, before battery fully seals, it is possible to use the suitable forming battery such as extruding.
The nonaqueous electrolytic solution secondary battery that the present invention provides, due to high power capacity, battery behavior is the best, it is possible to use so
Characteristic, can be used as mobile phone, removable information-based instrument such as notes wood computer etc. drive the secondary cell of power supply, and
And, extensively utilize as the power supply of the various machine such as electric automobile or hybrid electric vehicle.
Inventor finds with unremitting effort, by the electrode material constituted at sulfenyl materials such as elemental sulfurs through studying intensively
The transition metal powders such as middle addition copper powder, and this electrode material is used as negative electrode active material (the usual elemental sulfur of lithium-sulfur cell
Be considered as positive electrode always) can be greatly improved the cycle life of the sulfenyl materials such as elemental sulfur, and by this negative material with
In lithium ion battery, widely used positive electrode, barrier film, nonaqueous electrolytic solution etc. constitute high performance lithium ion battery, take
Obtained the achievement of the present invention.Described positive electrode includes that lithium ion can reversibly embed-lithium ion the oxo transition metal of deintercalation
Compound, as with cobalt acid lithium (LiCoO2), ternary material (LiNi1/3Co1/3Mn1/3O2) etc. for representative stratiform metal-oxide,
With LiMn2O4 (LiMn2O4) be the metal-oxide of the spinel-type of representative, with LiFePO4 (LiFePO4) it is the Fructus Canarii albi of representative
The metal-oxide etc. of stone-type.
In the present invention, the addition of the transition metal powders such as copper powder, electrode in charge and discharge process, the transition metal such as sulfur and copper
Reaction generates the new compound insoluble in electrolyte.The transition metal such as copper are improve the activity of sulfur-sulfide linkage and utilization rate
, also sulfur is fixed on electrode meanwhile, thus has fundamentally solved the technical problem that lithium-sulfur cell is intrinsic so that sulfur electricity
The performance in pond is greatly improved.In the electrode system or battery of the present invention, the utilization rate of elemental sulfur almost can arrive
100%, capacity can be existing cathode material of lithium ion battery graphite close to or up the theoretical capacity (1670mAh/g) of sulfur
More than 4 times.The battery of the present invention has the cycle performance of excellence, can be suitable with existing lithium ion battery.
The current potential of the negative electrode active material that the present invention provides is about 1.7V (relative to lithium metal current potential).Use this negative pole
The battery of active substance and respective negative, during charge and discharge cycles, will not produce Li dendrite in negative terminal surface, be possible to prevent
The internal short-circuit phenomenon caused because of Li dendrite.So using lithium metal or the biography of graphite of low potential with negative electrode active material
System lithium ion battery is compared, and the battery of the present invention is safer.On the other hand, the negative electrode active material of the present invention and employing spinelle
Type lithium titanate (Li4Ti5O12: current potential 1.5V, actual capacity about 150mAh/g), running voltage close, but the activity of the present invention
The theoretical capacity of material is more than 10 times of the latter.So utilizing the battery of the negative electrode active material of the present invention, than same safety
It is higher that the lithium titanate series lithium ion battery that property is high compares battery capacity.
The negative electrode active material that the present invention provides has that the performance similar with lithium titanate, i.e. discharge curve be smooth, electric conductivity
Good, good cycling stability.It addition, it also has the advantages such as wide material sources are cheap, preparation is easy, specific capacity is high.
Accompanying drawing explanation
Fig. 1 is the electrode charge and discharge curve of embodiment 1 negative pole.
Fig. 2 is the electrode charge and discharge curve of embodiment 1 positive pole.
Fig. 3 is the charging and discharging curve of embodiment 1 battery.
Fig. 4 is LiMn2O4/ Li battery and LiMn2O4/Cu-S8The cycle characteristics correlation curve of battery.
Detailed description of the invention
By embodiment, the present invention will be further described below in conjunction with the accompanying drawings.It is understood, however, that embodiment and contrast
Example is for explaining embodiment of the present invention, and in the range of without departing from present subject matter, scope is not by institute
State the restriction of embodiment.
Other purpose of the present invention and advantage will be set forth in part in the description which follows, partly from described explanation
It is clear that or understood by the enforcement of the present invention.
Further, in the following description, what " % " was not specifically noted is quality criteria.
Embodiment 1
Prepared by negative pole: the electrolytic copper powder (mol ratio Cu: S=2: 1) of 65g sulfur powder, 30g conductive agent acetylene black, 130g is ground
And mix homogeneously, in the CMC adhesive aqueous solution of the solid content 2% being then added to 100 grams, with Solvents N-methyl-2-pyrrolidine
Ketone (NMP) and distilled water are uniformly dispersed (volume ratio about 1:1), add the SBR adhesive emulsion that 7.5g solid content is 40%,
Mix and blend 1 hour or longer time, it is prepared as the powdery pulp of certain viscosity；Above-mentioned cathode size is coated on thickness 10 μm
In aluminum foil current collector, the electrode plates after coating is dried 12h in the vacuum drying oven of 60 DEG C and removes solvent, then by pole piece punching press
Become the disk of diameter 12mm, weigh, for the negative pole of battery.Sulfur content 1.4mg in this negative plate.Electrode discharge curve and putting
Capacitance is shown in Fig. 1.
Positive pole preparation is at the spinel lithium manganate (LiMn of 90 mass parts2O4, positive active material, actual capacity
In 106.3mAh/g), mix the white carbon black as conductive agent of 5 mass parts, add polyvinylidene fluoride 5 mass in the mixture
Part is dissolved in the solution of NMP, mixes and makes positive pole and close serosity so that it is by 70 eye mesh screens, remove the part that particle diameter is big.Should
On the one side of the aluminium foil that anode sizing agent is uniformly coated to thickness 15 μm, the electrode plates after coating is in the vacuum drying oven of 80 DEG C
After being dried 12h removing solvent, pole piece is struck out diameter 11mm disk, weighs, for the positive pole of battery.Active matter in positive pole
The content of matter according to the ratio of positive electrode capacity anticathode capacity be 100 than 120(i.e. negative pole excess) design, coating preparation.Electrode is put
Electricity curve and discharge capacity are shown in Fig. 2.
Battery preparation above-mentioned sulfur negative pole and above-mentioned spinel lithium manganese oxide anode pole piece form button cell to battery
Evaluated.The preparation method of battery is as follows: in the glove box of argon gas atmosphere, according to cathode pole piece, three layers of porous septum
(PP/PE/PP), the laminated structure of bibulous paper, anode pole piece, aluminium backing, add electrolyte and be assembled into the full battery of button, and at electricity
Testing the performance of battery in pond test system, discharge and recharge blanking voltage is 1.0V～2.6V.Putting of battery discharge curve and battery
Capacitance (due to negative pole excess, be the most also positive discharge capacity) is shown in Fig. 3 and Biao 1.
Electrode capacity confirms:
The electrode slice of preparation, diameter are bigger 1mm than electrode slice, thickness is the metallic lithium foil of 0.1mm, electrolyte (the two (three of 1M
Methyl fluoride sulfonic acid) imine lithium (LiTFSI)-DOL/DME(3/7 volume ratio)), and barrier film (PP/PE/PP), at full argon
Glove box assembles button half-cell.After placing an evening, utilize charge and discharge device that battery behavior is evaluated.The field of negative pole
Close, discharging condition: with 0.5mA/cm2Electric current will after battery constant-current discharge to 1.0V terminate；Charge condition: with 0.5mA/cm2
Electric current battery is charged to 3.0V；The occasion of positive pole, charge condition: with 0.5mA/cm2Electric current battery is charged to 4.3V；
Discharging condition: with 0.5mA/cm2Electric current will after battery constant-current discharge to 3.0V terminate.
The evaluation of battery charging and discharging performance:
The most first battery is charged, after full charge, carries out constant-current discharge again, anti-under similarity condition afterwards
Repeatedly circulate again.Charge condition: after battery being charged to certain voltage with the charging and discharging currents of 0.5C, then continue to fill under this voltage
It is (now for full charge) till 2.5 hours that electricity reaches total charging time；Discharging condition: battery is determined electricity with the discharge current of 1C
Terminate after flowing to certain voltage.Capability retention after 100 circulations of battery is the capacity after 100 cycle charge-discharges of battery
Ratio (%) with the capacity after first time cycle charge-discharge.
Comparative example 1
In the negative pole preparation process of embodiment 1, in addition to copper powder is substituted by graphitic carbon (the most not adding copper powder), with enforcement
Example 1 is prepared for LiMn equally2O4/S8Button cell, test the results are shown in Table 1.
Embodiment 2
In the negative pole preparation process of embodiment 1, except with positive active material ternary material ((LiNi1/3Co1/3Mn1/ 3O2) actual capacity 147.0mAh/g) positive pole substitutes beyond spinel lithium manganate, embodiment 2 is prepared for similarly to Example 1
LiNi1/3Co1/3Mn1/3O2/Cu-S8Button cell, test the results are shown in Table 1.The charging/discharging voltage scope of battery be 1.0V～
2.6V。
Fig. 1～3 be respectively negative pole, positive pole and the battery in embodiment 1 discharge curve.Negative pole as can be seen from Figure 1
Discharge platform be 1.7V before and after, first circle electric discharge unit sulfur gravimetric discharge capacities be up to 1477mAh/g, close to elemental sulfur material
Theoretical capacity.And the discharge capacity 262mAh/g utilization rate that do not adds the elemental sulfur in the battery of the comparative example 1 of copper powder is extremely low, table
The utilization rate of the compound elemental sulfur material that improve of bright elemental sulfur and copper powder.Fig. 3 can be regarded as the simple folded of Fig. 1 and Fig. 2
Adding, the mean voltage of discharge curve is 2.09V, and its specific discharge capacity is 101.3mAh/g, basically identical with the capacity of positive pole, says
Bright utilize Cu-S8Play the capacity of positive electrode as negative material well, and its reversible capacity is relatively low.Table 1 is implemented 2
In ternary material ((LiNi1/3Co1/3Mn1/3O2) actual capacity 147.0mAh/g) specific discharge capacity of battery that constitutes is
142.1mAh/g, consistent with the actual capacity of positive pole, illustrate to utilize Cu-S8Positive pole appearance has been played well as negative material
Amount, and its reversible capacity is less than positive electrode.
Fig. 4 is LiMn2O4/ Li battery and LiMn2O4/Cu-S8The cycle characteristics of battery compares, it can be seen that LiMn2O4/
Cu-S8Battery and LiMn2O4The cycle characteristics of/Li battery is basically identical, and through the circulation in 30 cycles, capability retention is 95%
Above, Cu-S is described8Negative material has charge/discharge cycle characteristics well.
The composition of table 1 battery and battery behavior
Embodiment 3～7
In the negative pole preparation process of embodiment 1, except substituting in addition to copper powder with the metal powder listed by table 2, embodiment 3～
7 are prepared for LiMn similarly to Example 12O4/M-S8(M is metal) button cell, test the results are shown in Table 2.
The composition of table 2 battery and battery behavior
It is not difficult to find out, described nickel, cobalt, molybdenum, the transition metal powders such as titanium or its partial oxidation utilized beyond copper or part
The compound of sulfuration is combined with elemental sulfur, all while improving the utilization rate of sulfur, improves the cycle characteristics of battery.
Embodiment 8
24g Na2S is dissolved in 50ml ethanol/water (1/1v/v) solution, is subsequently adding sulfur powder 10.8g, reacts 1 little under room temperature
Time, steam instrument with rotation and alcohol solvent evaporated, add 150ml DMF(dimethylformamide), stirring, then be slowly added dropwise
8.61g1,3-hexachlorobutadiene, reacts 1 hour under room temperature, adds 300ml water and makes product precipitate, centrifugal, successively with pure
Water, acetone, methanol clean.After 40 DEG C dry, obtain the solid carbon sulphur compound (CS of coffee color3.5)n。
Except with (CS3.5)nSubstitute elemental sulfur and (CS3.5)n: copper powder=1: 2(weight ratio) beyond, similarly to Example 1
It is prepared for cathode pole piece.Afterwards, above-mentioned negative pole is utilized to be prepared for LiMn similarly to Example 12O4/Cu-(CS3.5)nButton electricity
Pond, test the results are shown in Table 3.
Embodiment 9～10 and comparative example 2
In the negative pole preparation process of embodiment 8, except using the carbon sulphur compound listed by table 3 to substitute (CS3.5)nIn addition,
Embodiment 9～10 is prepared for LiMn similarly to Example 82O4/Cu-(CSx)nButton cell, test the results are shown in Table 3.
Not adding copper powder in the negative pole used in comparative example 2, other is the same as in Example 8.That tests the results are shown in Table 3.
The composition of table 3 battery and battery behavior
It can be seen that as elemental sulfur negative pole, the interpolation of copper powder substantially increases the same of the utilization rate of carbon sulphur compound
Time, improve the cycle characteristics of battery.
Although the present invention being described in detail with reference to preferred embodiment, but, those skilled in the art
Should be appreciated that can many modifications may be made or replaces, and without departing from appended claims or its equivalent to the present invention
The spirit and scope of the present invention illustrated.
Claims (11)
1. a battery cathode active substance, it is characterised in that this negative electrode active material contains at least one sulfenyl material and one
Plant transition metal powders.
Negative electrode active material the most according to claim 1, it is characterised in that described sulfenyl material is sulfur simple substance, organic sulfur
Compound or inorganic sulphide.
Negative electrode active material the most according to claim 1, it is characterised in that described sulfenyl material is Li2Sn、n≥1。
Negative electrode active material the most according to claim 1, it is characterised in that described transition metal powders include selected from Sc,
In Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Ta, W, Re, Os, Ir, Pt and Au
The elemental metals powder of a kind of element or the alloyed metal powder of several element, also include described elemental metals powder or alloy gold
Belong to powder partial oxidation or the product of partial vulcanization.
Negative electrode active material the most according to claim 2, it is characterised in that containing elemental sulfur and metallic copper powder.
Negative electrode active material the most according to claim 2, it is characterised in that containing carbon sulphur compound and metallic copper powder.
Negative electrode active material the most according to claim 3, it is characterised in that containing Li2Sn, n >=8 and metallic copper powder.
8. a battery cathode, including conductive current collector, conductive agent and binding agent, it is characterised in that also include claim 1-7
Negative electrode active material described in any claim.
9. a battery, including positive pole, porous septum and nonaqueous electrolytic solution, it is characterised in that also include described in claim 8
Negative pole.
Battery the most according to claim 9, it is characterised in that the solvent of described nonaqueous electrolytic solution be molecular formula be R
(CH2CH2O)nMany ethers of-R', wherein, n=1-6, R and R' are methyl or ethyl.
11. batteries according to claim 9, it is characterised in that the solvent of described nonaqueous electrolytic solution be dimethyl ether tetraethylene glycol (TEG),
Glycol dimethyl ether or 1,3-dioxolane.
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