CN1688063A - High specific capacity secondary lithium ion cell - Google Patents

High specific capacity secondary lithium ion cell Download PDF

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Publication number
CN1688063A
CN1688063A CNA2005100344804A CN200510034480A CN1688063A CN 1688063 A CN1688063 A CN 1688063A CN A2005100344804 A CNA2005100344804 A CN A2005100344804A CN 200510034480 A CN200510034480 A CN 200510034480A CN 1688063 A CN1688063 A CN 1688063A
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negative
oxide
lithium ion
battery
active material
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王洪
郭春泰
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Huizhou TCL Jinneng Battery Co Ltd
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Huizhou TCL Jinneng Battery Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

A high-specific capacity secondary Li ionic battery includes a shell containing an electrolyte bag, a positive, a membrane and a negative, among which, the positive is composed of a positive collector and Li compound oxide attached to its surface, the negative is composed of a negative collector and adsorption and de-adsorption Li ionic substance containing inactive oxide fast ions adhered on its surface, thickness of the active substance adhered on the negative surface is 0.03-0.30mm, the weight ratio of the inactive oxide fast ions playing the role of a conductor and the negative active substance is 0.01-1.0:100, the mean diameter of the ions is 10-300nm. When using as active material to fill in a thick electrode with high density, an inorganic oxide fast ionic conductor is applied to the negative to improve the Li ionic transmission efficiency from the active substance to the negative surface.

Description

A kind of high specific capacity secondary lithium ion cell
Technical field
The present invention relates to a kind of high specific capacity secondary lithium ion cell, refer in particular to a kind of high specific capacity secondary lithium ion cell that in negative pole, contains the fast ion of inorganic oxide that does not participate in discharging and recharging reaction.
Background technology
The raising of the integrated level of various mobile electronic products and the increase of function, also increasing to the requirement of battery capacity.Because the negative pole of secondary metals lithium battery is to be made by lithium metal or its alloy, and the theoretical specific capacity of lithium metal is about ten times of conventional carbon negative pole material graphite, therefore become in recent years a focus as the research of the lithium secondary battery of negative pole with lithium metal.The structure of common this secondary lithium battery is, the positive pole that is formed as active material by lithium-contained composite oxide, by absorbing and take off negative pole, barrier film and the electrolyte that the material of inhaling lithium ion constitutes.Along with the maturation of research, lithium ion battery is widely used in current as in the various mobile electronic products such as mobile phone, laptop computer, portable DVD player, MP3, PDA, blue tooth earphone, model plane, interstellar vehicle, military applications and mobile base station with its high specific energy, good cycle performance, high operating voltage and good cryogenic property.
But present stage, the utilance of lithium ion battery positive and negative electrode reached its limit 100% substantially, to improve energy density again, just can only adopt as back method, 1. replace original active matter with the active matter of new higher energy density, 2. increase the obturator density of active material in the pole plate, 3. increase the thickness of pole plate.At this, as adopt new active matter, then the discharge proterties because of battery changes, and causes the circuit of the equipment that uses this novel battery to redesign, so this novel battery can not be used for the now general electrical equipment by the conventional batteries design; Therefore, have only, reduce the ratio of inert matter such as collector or barrier film in other words, reach the high-energy-density of battery by increasing the thickness of both positive and negative polarity active matter obturator density or increase electrode.Yet along with electrode is loaded the volume density increase, its hole descends; Thickness increases, and electrolyte just can not transmit lithium ion fast, so the filling volume density of excessive increase pole piece thickness or excessive increase active material, meeting influence the charge-discharge performance, particularly high-rate charge-discharge capability of battery greatly.And the viscosity of electrolyte when low temperature increases, the decline that the charge-discharge performance of electrode can be bigger, and the utilance of positive and negative electrode active material may drop to the 20-30% level like this, and final actual energy density reduces.
This shows that crucial problem is to improve the performance of electrode.How to improve cycle performance, the Japan Patent 7-153495 of unexamined proposes to add some inactive additive such as Al in positive pole 2O 3, In 2O 3, SnO 2, ZnO.The Japan Patent 10-188957 of unexamined and 7-73969 propose to add some porous inorganic particles in the negative pole of being made of active material/carbon.In order to improve high-rate discharge ability, the Japan Patent 10-255807 suggestion of unexamined adds ceramic masses Al 2O 3, SiO 2, ZrO 2With MgO and Na 2O is to being in the negative pole of active matter with the charcoal.Take the filling volume density and the thickness of electrode are increased in order to improve energy density, the porosity of electrode is descended, hinder the infiltration of electrolyte, cause the conductivity of lithium ion to descend, cause active material in the electrode effectively not identify oneself with to discharge and recharge in the reaction and go.Even at this moment added above-mentioned these additives in electrode, the charge-discharge performance of battery, particularly high-multiplying power discharge and cryogenic property still have bigger decline.And in order to improve the infiltration of electrolyte, a possible method is the porosity that increases electrode, but the increase of porosity makes pole strength descend naturally, also can cause between the electrode interior active matter and separate.On the other hand, if increase amount of binder, to increase mechanical strength, the energy density of electrode can descend again.
Summary of the invention
The problem that the present invention need solve is to seek a kind of half-way house, solves a difficult problem that exists in the above-mentioned prior art with a kind of secondary lithium battery with high-energy-density and excellent cycle performance.
Designed a kind of high specific capacity secondary lithium ion cell according to the above-mentioned problem that needs to solve, comprise battery container, be provided with the bag of splendid attire electrolyte in the battery container and be immersed in positive pole in the electrolyte, negative pole, be positioned at the barrier film that between both positive and negative polarity both positive and negative polarity is separated, anodal by plus plate current-collecting body and attached to surface, plus plate current-collecting body one or both sides positive active material---lithium-contained composite oxide is formed, negative pole is by negative current collector and attached to the negative electrode active material of negative pole currect collecting surface---absorption and desorption lithium ion material are formed, and adsorb and the negative electrode active material of desorption lithium ion material in contain nonactive oxide and reach the ion that ionization goes out from this oxide---as the fast ion of conductor.This plays conductor---and the fast ion of nonactive oxide of conduction and the weight ratio wt between negative electrode active material are 0.01～1.0: 100; The mean particle diameter of the fast ion of nonactive oxide is 10～300 nanometers.Wherein, the oxide that relates in the fast ion of nonactive oxide is meant strontium titanates SrTiO 3, zirconia titanate ZrTiO 3, sodium silicoaluminate NaAlSiOx 4, lithium aluminosilicate LiAlSiO 4, titanium oxide lanthana lithia compound Li 0.2La 0.6TiO 3And lanthanum acid calcium lithium niobate compound Li 4CaLa 2Nb 2O 12, lanthanum acid strontium lithium niobate compound Li 4SrLa 2Nb 2O 12, lanthanum acid barium lithium niobate compound Li 4BaLa 2Nb 2O 12In one or more mixture.In addition, the thickness of the active material that adheres on the negative terminal surface is 0.03～0.30 millimeter.
Be that as can be known, positive active material can be any lithium-contained composite oxide, as strontium titanates SrTiO from related known technology what this need further specify 3, zirconia titanate ZrTiO 3, sodium silicoaluminate NaAlSiO 4, lithium aluminosilicate LiAlSiO 4, titanium oxide lanthana lithia compound Li 0.2La 0.6TiO 3And lanthanum acid calcium lithium niobate compound Li 4CaLa 2Nb 2O 12, lanthanum acid strontium lithium niobate compound Li 4SrLa 2Nb 2O 12, lanthanum acid barium lithium niobate compound Li 4BaLa 2Nb 2O 12, they can be singly with also mixing usefulness.Also contain in the positive active material of anodal surface attachment just like conductive agents such as acetylene blacks, the weight ratio between conductive agent and positive active material is 1～10: 100, and this conductive agent and ratio thereof are equally applicable to negative pole; Adhesive then is stable as butadiene-styrene rubber, fluororesin partially in electrolyte, materials such as tetrafluoroethylene resin, and the weight ratio between adhesive and positive active material is 1～10: 100, this adhesive and ratio thereof are equally applicable to negative pole.Wherein, plus plate current-collecting body can be aluminium, stainless steel or titanium metal foil or sheet metal, and negative current collector optional can be copper, stainless steel or nickel metal forming or sheet metal, collector thickness is generally 10～30 microns.
The active material of negative terminal surface is any adsorbable and take off the material of absorption lithium ion, as graphite, comprise Delanium, native graphite, graphitized carbon fibre.Silicon Si, tin Sn, aluminium Al, boron, germanium Ge, phosphorus P, plumbous Pb and alloy and oxide.
The barrier film that uses can be any high intensity, porous film, as the vistanex of porous; In addition, a kind of lithium ion conducting gel of being made up of polymer-matrix and the electrolyte in impregnated in also can be used as barrier film.Shell can adopt any material known in the related process, the aluminum-plastic composite membrane that is composited as aluminium foil and thermoplastic resin and aluminum metal shell etc.
Electrolyte is organic electrolyte, and the solute and the organic solvent combination that are usually used in the secondary lithium battery all can be selected for use, as lithium salts being dissolved in the electrolyte in ring-type and the non-annularity carbonic ester, and will be as the phosphorofluoric acid lithium LiPF of solute 6Be dissolved in the electrolyte of making among mixed solvent ethylene carbonate EC, diethyl carbonate DEC and the methyl ethyl carbonate EMC.
During making, to positive pole can be at plus plate current-collecting body one-sided or both sides coating positive active material.When in the coating of anodal both sides, multilayer positive pole, negative pole can be compound to barrier film, positive pole, and negative pole, the combination of collector can directly be loaded in the shell, in the shell of packing into after also can reeling.
What this need state be, though it is overlapping that the range of choice of the active material of oxide that adds in the negative terminal surface adhesion layer and anodal surface attachment layer may occur, but should be noted that, make sure to keep in mind to select identical material or material in practical operation, the used otide containing lighium thing of promptly anodal used lithium-contained composite oxide and negative pole is a material not of the same race.
Because in the active material of negative terminal surface of the present invention, contain nonactive oxide, fast ion in this nonactive oxide has the high-lithium ion affinity, so lithium ion optionally transmits the surperficial of fast ion or between the interface of fast ion and electrolyte, rather than the electrolyte that passes through that usually occurs in the electrode transmits lithium ion.Therefore, even load at electrode activity object height volume under the situation of density, can effectively improve lithium ion transmission and efficiency of transmission from the active matter surface to electrode surface by in battery lead plate, adding nonactive oxide selectively.Certainly, nonactive oxide need have the excellent anticathode active matter and the stability of electrolyte, excellent electrochemistry and thermal stability and low water absorption and hydrolytic stability are arranged in operating voltage range, and its adding can not damage the performance of electrode.In addition, owing to can not set up local microbattery configurations between nonactive oxide and active material, be that nonactive oxide does not participate in discharging and recharging course of reaction, can not discharge lithium ion and give electrode in the electrochemical reversible mode, can not absorb lithium ion from electrode yet, so contain nonactive oxide in the negative pole, the capacity of its battery lead plate can not reduce yet.
Embodiment
Thinking of the present invention provides a kind of secondary lithium battery, it consists of the positive pole of lithium-contained composite oxide, contain the negative pole that can absorb and take off the absorption negative active core-shell material of lithium ion and nonactive inorganic oxide (with the ion of this oxide as the fast ion of conductor), organic electrolyte, place the barrier film of negative positive interpolar, this kind battery structure mainly is aimed at and uses active material to load the higher thick electrode of density, being about to a kind of inorganic oxide that does not participate in discharging and recharging reaction joins in the negative pole, utilize its fast ion as conductor (conductor), to improve the lithium ion efficiency of transmission from the active material to the electrode surface.
Realize that the positive pole and the diaphragm material that use in the process of the present invention are now known material and technology as described above, the material and the principle of negative pole are also addressed, just repeat no more at this.The making of following anticathode and effect are further elaborated and cooperate specific embodiment to be compared with test data.
Owing to add the oxide of negative pole mixture high lithium ion affinity is arranged, so lithium ion optionally transmits between the interface of the surface of oxide or oxide and electrolyte, rather than the electrolyte that passes through that usually occurs in the conventional electrodes transmits lithium ion.Given this, even load at electrode activity object height volume under the situation of density, the lithium ion transmission that improves from the active matter surface to electrode surface by interpolation oxide in battery lead plate also is possible.
During enforcement, the particle mean size of oxide is advisable with 10～300 nanometers.When particle diameter during less than 10 nanometers, the particle of oxide can produce and gather, and at this moment particle will be evenly spread in the negative terminal surface adhesion layer very difficult; And when when particle diameter during greater than 300 nanometers, also be difficult to it is evenly spread in the negative terminal surface adhesion layer, just reduced by adding the effect that oxide improves the lithium ion transmission thus; In addition, the particle diameter of oxide may pass through laser scattering method, surveys factually, when being uniformly distributed in the oxide particle of particle diameter 10～300 nanometers in the adhesion layer, even lithium ion can both effectively transmit in electrolyte content electrode layer seldom.
The amount of the amount of oxide and surface reactive material is 0.01～1: 100 by weight wt meter value in the adhesion layer of negative pole.As will greatly reduce the filling volume density of active matter greater than 1 part amount; When being lower than 0.01 part, oxide will be not enough to be scattered in equably in the adhesion layer, and this also will reduce the effect of lithium ion transitivity.
The thickness of negative el also has bigger influence to fast ion in the transmission of electrolyte, 0.08～0.5 millimeter of the thickness value of negative pole.When negative el (comprising the surface attachment layer) was thin, the distance that electrolyte and fast ion move between electrode pad was just short, and the lithium ion transmission in the entire electrode plate is smooth, and speed is also enough fast.But, add the effect that oxide produced and just be difficult to manifest when negative electrode plate thickness during less than 0.08 millimeter.During when the increase of negative el (comprising the surface attachment layer) thickness and greater than 0.5 millimeter, the path that electrolyte and fast ion move between electrode pad is elongated, and can't arrive the entire electrode plate, the oxide that is present in the negative pole does not have the effect that lithium ion transmits that improves in electrode, and the mechanical strength of battery lead plate reduces, cause pole plate to separate, make cycle performance and battery reliability decrease with the surface attachment layer.And in 0.08～0.5 millimeter interval, even electrolyte does not soak into the entire electrode plate, the oxide that is dispersed in the battery lead plate can allow lithium ion penetrate battery lead plate easily, reach active material wherein, and along with the increase of battery lead plate thickness, the effect that improves the lithium ion transmission effect by oxide is obvious more.Need to prove, the thickness of negative electrode comprises collector and the attachment coating on it, the thickness that promptly comprises the adhesion layer of active material and oxide is 0.03～0.30 millimeter, when 0.1～0.25 millimeter of the one-tenth-value thickness 1/10 value of adhesion layer on the electrode, the laser propagation effect of above-mentioned lithium ion is very obvious.
When making negative pole, for improve oxide to the stability of organic electrolyte and in electrode is made the dispersiveness of oxide in adhesion layer, with the affinity of adhesive, to in being higher than 300 ℃ environment, handle or it is carried out surface treatment, make its surface hydrophobicity or give the affinity of its surface organic electrolyte with organic substance to oxide.At this moment, big even the battery lead plate plate thickness reaches the filling volume density of electrode greatly, the adding of otide containing lighium thing in the negative pole also can improve the transmission of lithium ion from the electrode active material surface to electrode surface.This is that the oxide that is dispersed in the electrode is transferred to the active material that is scattered in the entire electrode by lithium ion, makes all active matter mass-energy effectively identify oneself with to discharge and recharge in the reaction and goes because some position of electrode may not contain electrolyte.So negative pole is when high energy density, cycle performance can improve.And after the lithium ion transport property improved, other performance such as high-multiplying power discharge and cryogenic property also were enhanced.
Be specific embodiment below.
Example 1.Listed various oxides have prepared the secondary lithium battery shown in the table in the chart-1, and assess with the utilance of negative electrode active material; The utilance here refers to the percentage of the 5th discharge capacity of battery and theoretical capacity.
Battery preparation method:
1, negative pole manufacturing: to be negative electrode active material mix with oxide (following represent with Y) in the table-1 native graphite, and the native graphite particle diameter is 18 μ m, and the average grain diameter of Y is 70nm.The amount of Y is to contain 0.3 part of weight in 100 parts of active matters, and the mixture that obtains is an adhesive with the butadiene styrene resin aqueous liquid dispersion, and the aqueous solution of carboxyl methyl cellulose is that intensifier is made slurry.Active matter, adhesive, the ratio of thickener is 97: 2: 1.The gained slurry is applied to the thick Copper Foil two sides of 20 μ m, and the two sides is of uniform thickness, sheet is rolled with milling train in dry back, again in nitrogen N 2In in 200 ℃ down dry, be washed into negative plate then, the pole pieces of 8 material samples that are washed into are numbered with 1-8# successively.
Load density by the volume that pole piece calculates negative electrode active material with the weight of active material (Delanium) in attachment material layer volume and the attachment layer, come theory of computation capacity by the weight of Delanium and the capacity of Delanium (320mAh/g).
2, positive plate manufacturing: LiCoO 2Mix with the acetylene black as conductive agent, attachment material mixes with PVDF/NMP solution as adhesive, makes anodal composite material slip.Active matter, conductive agent and binder wt ratio are 95: 2: 3.
The anodal attachment chylema of gained is imposed on thick aluminium foil surface one side of 20 μ m, and drying obtains the anodal attachment material layer of one deck, and sheet is rolled with milling train in dry back.Anodal rolling thickness is 3.6g/cm with the filling bulk density that keeps anodal attachment material 3Be as the criterion.The positive plate that rolls behind the sheet obtains positive plate in 200 ℃ of dry backs with the sheet-punching machine punching.The content of positive plate will be adjusted to bigger than negative plate, so that battery capacity can be owing to positive pole is limited to influence the capacity of negative plates performance in the loop test in the back.
3, battery assembling: the electrode assembling is that positive/negative plate is folded into together at interval, and is middle with the thick PE perforated membrane access node of 20 μ M.Combination of electrodes after the assembling is packed in the plastic-aluminum packaging film pocket, and plus plate current-collecting body is grouped together, and the terminal of formation is guided to outside the shell by the opening part of pack case.Same, the terminal that negative current collector forms is drawn out to outside the shell by another opening.
LiPF6 is dissolved in EC/DEC/EMC (2: 2: 3), and LiPF6 concentration is 1.0M/L, make electrolyte after, inject the electrolyte into pocket.At last, under the condition of vacuumizing, with opening heat-sealing (thermal weld).
Use said method, the negative material that contains various different oxide Y in table-1 has been made battery 1-8.For relatively, be shaped on another battery C-1 with quadrat method, this battery oxide-free " Y ", this battery mark is " being used for the comparison battery ".
4, negative pole utilance assessment: every battery is all 0.2C (under this multiplying power, theoretical capacity is for filling discharge in 5 hours 5 hours).3.0V-4.2V voltage range charges and discharge 5 times repeatedly.Calculate the discharge capacity of the 5th circulation.Calculate the utilance of negative material by the 5th discharge capacity and theoretical capacity.In the assessment, discharge and recharge all and carry out for 20 ℃ at normal temperature, what obtain the results are shown in table-1, and negative pole thickness (containing the attachment layer) and porosity are also listed in the table.
Table-1
Oxide " Y " Negative pole thick (mm) Porosity (%) Negative pole utilance %)
????B-1# ????LiAlSiO 4 ????0.130 ????30 ????88
????B-2# ????SrTiO 3 ????0.125 ????28 ????86
????B-3# ????ZrTiO 3 ????0.135 ????27 ????91
????B-4# ????Li 0.2La 0.6TO 3 ????0.140 ????26 ????91
????B-5# ????Li 4SrLa 2Nb 2O 12 ????0.140 ????28 ????89
????B-6# ????Li 4BaLa 2Nb 2O 12 ????0.135 ????29 ????93
????B-7# ????Li 4CaLa 2Nb 2O 12 ????0.130 ????31 ????94
????B-8# ????NaAlSiO 4 ????0.135 ????27 ????90
????C-1# ????none ????0.130 ????31 ????64
Can see that battery 1-8 can have a kind of different oxide " Y " in every battery cathode from table-1, its negative pole utilance is all greater than 80%, and only is 64% as the battery utilance of the oxide-free Y of reference.
Example 2.Battery 9-12# uses with the same quadrat method of example 1 with comparison battery C2-C3 and makes.Difference is in only using oxide LiAlSiO 4As Y, but the granularity of Y has nothing in common with each other, as table-2.Utilance is also used with example 1 identical method and is assessed, and the result is as table-2.The thickness and the porosity of negative pole also have been described in the table-2.
Table-2
Oxide " Y " median particle (μ m) Negative pole thick (mm) Porosity (%) Negative pole utilance (%)
????C-2# ????0.005 ????0.135 ????30 ????67
????B-9# ????0.04 ????0.130 ????28 ????88
????B-10# ????0.07 ????0.135 ????27 ????91
????B-11# ????0.2 ????0.140 ????26 ????91
????B-12# ????0.3 ????0.140 ????28 ????89
????C-3# ????0.5 ????0.135 ????29 ????71
As table-2 results, the LiAlSiO that the 9-12# battery contains 4Particle diameter have from 10-300nm and be not less than 88% utilance.And the C-2 of battery contains the Y of 0.005 μ m as a comparison, and the negative pole utilance that C-3 contains the Y of 0.5 μ m particle diameter but has only 67% and 71%.The negative pole of C-2 and C-3 battery is cut, tangent plane is carried out ESEM method sem analysis, find that wherein secondary aggregation has taken place the particle of oxide Y, (dispersion) evenly do not distributed.
Example 3.13-17 battery use-case 1 same procedure is made, except LiAlSiO 4Particle diameter be that the weight of the oxide Y in 0.07 μ m and the per 100 parts of negative electrode active materials is different, as at table-3, as a comparison, made relatively battery C-4, do not contain oxide Y among the C-4.The negative pole utilance of every battery is assessed the same procedure of use-case 1, and display list-3 is shown-3 and listed negative pole thickness and porosity equally as a result.
Table-3
Y umber/per 100 parts of negative electrode active materials Negative pole thick (mm) Porosity (%) Negative pole utilance (%)
????C-4# ????none ????0.135 ????31 ????64
????B-13# ????0.005 ????0.130 ????28 ????75
????B-14# ????0.01 ????0.135 ????27 ????83
????B-15# ????0.1 ????0.140 ????26 ????91
????B-16# ????1 ????0.135 ????28 ????88
????B-17# ????3 ????0.140 ????29 ????74
As table-3 results, the 13-17 battery is compared with comparing battery C-4, and the negative pole utilance improves, and particularly the 14-16 battery contains LiAlSiO 40.01-1 part/100 parts of negative electrode active materials, the negative electrode active material utilance is not less than 83%.
Example 4.The 18-24 battery is made with method in the example 1, contains LiAlSiO 4Particle diameter change 0.07 μ m into, the Y addition is 0.3 part/100 parts negative electrode active materials, and the thickness of negative pole (mixture layer) difference.As table-4, as a comparison, made relatively battery C-5, C-5 does not contain LiAlSiO 4, negative pole is thick to be 0.145 μ m, the negative pole utilance is with example-1 same method evaluation.As a result, as table-4, electrode porosity and the 5th discharge capacity have also been listed in this.
Table-4
Negative pole thick (mm) Discharge capacity (mAh/cm 2) Porosity (%) Negative pole utilance (%)
????B-18# ????0.04 ????7 ????28 ????88
????B-19# ????0.09 ????14 ????26 ????95
????B-20# ????0.14 ????22 ????26 ????89
????B-21# ????0.25 ????39 ????27 ????86
????B-22# ????0.40 ????62 ????28 ????82
????B-23# ????0.50 ????91 ????28 ????80
????B-24# ????1.0 ????55 ????30 ????30
????C-5# ????0.145 ????21 ????32 ????83
As everyone knows, during electrode oxide-free Y, increase with battery lead plate thickness, the negative pole utilance descends.Yet, find out that from table-4 the negative pole utilance of 19-23 battery is no less than 80%.The negative pole of No. 24 batteries is that 1.0mm is thick, and its utilance has only 30%.Because the electrode mechanical strength is low, the attachment layer may separate and comes off.
No. 18 battery cathode utilances of the thick 0.04mm of negative pole do not contain LiAlSiO with relatively battery C-5 is suitable among the C-5 4, this explanation oxide Y creates improves effect and can not embody in No. 18 batteries.
Go up routine result and clearly demonstrate, negative pole thickness is preferably between 0.08-0.5mm, and single mixture layer thickness is at 0.03-0.24mm.
Though can not be quantitative because the mechanical strength of pole plate is not tested, the mechanical strength of battery 19-23 number battery lead plate increases with the thickness minimizing of pole piece.Yet, even if the electrode of battery 20-23 all has the similar identical mechanical strength of C-5.This shows that oxide Y not only improves the transmission of electrode intermediate ion, also improves the mechanical strength of pole plate.So oxide Y joins in the negative pole mixture layer, can stop owing to mixture breaks away from the internal short-circuit that causes from electrode, the cycle performance of battery and reliability are improved.
Example 5.25-28 battery and C-6, C-7 makes from example 1 method, just " Y " is changed into Li 4SrLa 2Nb 2O 12The particle diameter difference of its Y is as table-5.The negative pole utilance is also equally assessed with example 1, the results are shown in table-5, and the thickness of negative pole and porosity are also listed in table-5.
Table-5
Oxide " Y " particle mean size (μ m) Negative pole thick (mm) Porosity (%) Negative pole utilance (%)
????C-6# ????0.004 ????0.135 ????30 ????62
????B-25# ????0.01 ????0.130 ????28 ????91
????B-26# ????0.04 ????0.135 ????27 ????93
????B-27# ????0.2 ????0.145 ????26 ????90
????B-28# ????0.3 ????0.140 ????28 ????85
????C-7# ????0.5 ????0.135 ????29 ????68
By table-5 as can be known, contain the Li that particle diameter is 10-300nm 4SrLa 2Nb 2O 12The negative electrode active material utilance of battery 25-28 be no less than 85%, and contain particle diameter 4nm Li 4SrLa 2Nb 2O 12Battery C-6 and contain particle diameter 0.5 μ m Li 4SrLa 2Nb 2O 12The C-7 battery, its negative electrode active material utilance is 62% and 68%.The negative pole of C-6 and C-7 is cut, it is used the scanning electron microscope sem analysis, see that secondary aggregation has taken place the particle of oxide Y therein, can not in the negative pole mixture, evenly disperse.
Example 6.Battery 29-33 and relatively battery C-8 use with the method for example 1 and make, except with Li 4SrLa 2Nb 2O 12As otide containing lighium thing Y, Li 4SrLa 2Nb 2O 12Granularity be 0.07 μ m, the amount difference of 100 parts of pairing Y of negative electrode active material, as the table-6.The negative pole utilance is with calculating with example 1 identical method, and the result is shown in table-6.The thickness and the porosity of negative pole are also listed in table-6.
Table-6
Y umber/per 100 parts of negative electrode active materials Negative pole thick (mm) Porosity (%) Negative pole utilance (%)
????C-8# ????none ????0.35 ????31 ????64
????B-29# ????0.005 ????0.130 ????28 ????73
????B-30# ????0.01 ????0.135 ????27 ????81
????B-31# ????0.1 ????0.140 ????26 ????88
????B-32# ????1 ????0.135 ????28 ????85
????B-33# ????3 ????0.140 ????29 ????74
Shown in table-6, battery 29-33 is with respect to C-8, and the negative pole utilance is improved.Particularly contain Li 4SrLa 2Nb 2O 120.01-1 the battery 30-32 of deal, the negative active core-shell material utilance is not less than 81%.
Example 7.Battery 34-40 uses with example 1 the same method and makes, except Li 4SrLa 2Nb 2O 12Viscosity be 0.07 μ m, the Li that adds in per 100 parts of negative electrode active materials 4SrLa 2Nb 2O 12It is 0.3 part.The thickness of battery cathode has nothing in common with each other, and as table-7, for relatively, has made relatively battery C-9.C-9 does not contain Li 4SrLa 2Nb 2O 12, negative pole thickness is 0.13 μ m.The assessment of battery utilance use-case 1 same procedure the results are shown in table-7 in this example, and the discharge content and the porosity of negative pole are also listed in wherein.
Table-7
Negative pole thick (mm) Discharge capacity (mAh/cm 2) Porosity (%) Negative pole utilance (%)
????B-34# ????0.04 ????7 ????28 ????89
????B-35# ????0.09 ????14 ????26 ????90
????B-36# ????0.13 ????22 ????26 ????91
????B-37# ????0.27 ????39 ????27 ????88
????B-38# ????0.38 ????62 ????28 ????87
????B-39# ????0.50 ????91 ????28 ????80
????B-40# ????1.0 ????55 ????30 ????30
????C-9# ????0.13 ????21 ????32 ????83
As described in table-7, battery 35-39 has and is not less than 80% negative pole utilance, and battery 40, and negative pole thickness is 1.0mm, and the negative pole utilance is 30%, and this is because the electrode mechanical strength is low, and the negative pole mixture layer separates to come off and causes.
Battery 34, negative pole thickness are 0.04mm, its negative pole utilance with do not add Li 4SrLa 2Nb 2O 12Battery C-9 equate, show that the effect that Y at this moment promotes the negative pole utilance does not embody.
Can know from above-mentioned example and to know that the thickness of negative pole is preferably in 0.08-0.5mm, the thickness of negative pole mixture layer is preferably in 0.24-0.03mm (single face).
Can not be quantitative though do not survey mechanical strength, visible battery 35-39 increases with thickness of electrode, and the electrode mechanical strength reduces.Even if yet like this, battery 38 and 39 electrode mechanical strength are almost still suitable with battery C-9, this explanation oxide Y not only increases the lithium ion transfer rate, and improves the negative pole mechanical strength.Therefore, otide containing lighium thing Y is added in the negative material mixture layer, can stop because negative electrode active material comes off and the internal short-circuit of carrying-off, thereby improve cycle performance, improves the functional reliability of battery.
Above routine 1-11 LiCoO 2Be positive electrode active material, Delanium and silicon alloy (NiS 2Cladding Si) as negative electrode active material.But use other positive electrode and negative material, also can reach the same effect of improving.Other positive electrode comprises LiNiO 2, Li 2Mn 2O 4, LiMnO 2And LiV 3O 8, can singly use, also can mix use.Other negative electrode active material comprises char-forming material, native graphite, graphitized carbon fibre.Si, Sn, Al, B, Ge, P, Pb, alloy and oxide.
With regard to adhesive, the stable material in electrolyte in the example of the present invention beyond the adhesive is all available.
Similar, other electrolyte and organic solvent combination that is used for serondary lithium battery all can be elected to be electrolyte, and when barrier film was the lithium ion conducting gel, these electrolyte also can be used.
Though this patent only has above-mentioned example, the thought of patent is not limited to these example scopes.

Claims (6)

1, a kind of high specific capacity secondary lithium ion cell, comprise battery container, be provided with the bag of splendid attire electrolyte in the battery container and be immersed in positive pole, negative pole in the electrolyte, be positioned at the barrier film that between both positive and negative polarity both positive and negative polarity is separated, anodal by plus plate current-collecting body and attached to surface, plus plate current-collecting body one or both sides positive active material---lithium-contained composite oxide is formed, negative pole is by negative current collector and attached to the negative electrode active material of negative pole currect collecting surface---and absorption and desorption lithium ion material are formed, and it is characterized in that
Contain nonactive oxide in the negative electrode active material of absorption and desorption lithium ion material and reach the ion that ionization goes out from this oxide---as the fast ion of conductor.
2, high specific capacity secondary lithium ion cell according to claim 1 is characterized in that describedly playing the fast ion of nonactive oxide of conductor effect and the weight ratio wt between negative electrode active material is 0.01～1.0: 100.
3, high specific capacity secondary lithium ion cell according to claim 2, the mean particle diameter that it is characterized in that the fast ion of nonactive oxide is 10～300 nanometers.
4,, it is characterized in that the oxide that relates in the fast ion of described nonactive oxide is meant titanium oxide lanthana lithia compound Li according to claim 1 or 2 or 3 described high specific capacity secondary lithium ion cells 0.2La 0.6TiO 3, strontium titanates SrTiO 3, zirconia titanate ZrTiO 3, sodium silicoaluminate NaAlSiO 4, lithium aluminosilicate LiAlSiO 4And lanthanum acid calcium lithium niobate compound Li 4CaLa 2Nb 2O 12, lanthanum acid strontium lithium niobate compound Li 4SrLa 2Nb 2O 12, lanthanum acid barium lithium niobate compound Li 4BaLa 2Nb 2O 12In one or more mixture.
5,, it is characterized in that the thickness of the active material that adheres on the negative terminal surface is 0.03～0.30 millimeter according to claim 1 or 2 or 3 described high specific capacity secondary lithium ion cells.
6, high specific capacity secondary lithium ion cell according to claim 5 is characterized in that the preferred thickness value of the active material that adheres on the negative terminal surface is 0.1～0.25 millimeter.
CNA2005100344804A 2005-04-27 2005-04-27 High specific capacity secondary lithium ion cell Pending CN1688063A (en)

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