CN103700880A - Lithium ion battery - Google Patents
Lithium ion battery Download PDFInfo
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- CN103700880A CN103700880A CN201210369008.6A CN201210369008A CN103700880A CN 103700880 A CN103700880 A CN 103700880A CN 201210369008 A CN201210369008 A CN 201210369008A CN 103700880 A CN103700880 A CN 103700880A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
- H01M4/405—Alloys based on lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a lithium ion battery. The lithium ion battery comprises a shell, and an electrode group and an electrolyte which are sealed in the shell, the electrode group comprises a positive electrode, a negative electrode and a diaphragm positioned between the positive electrode and the negative electrode, a positive material layer comprises a lithium iron phosphate positive active material, iron phosphate, a conductive agent and a positive binder; the smallest particle size of the iron phosphate is not lower than 20mum; a negative material layer comprises a negative active material layer, and the negative active material layer comprises lithium and/or a lithium alloy, a negative active material and a negative binder; or the negative material layer comprises the negative active material layer and lithium and/or the lithium alloy adhered to the negative active material layer, and the negative active material layer comprises the negative active material and the negative binder; and the negative active material comprises graphite and lithium titanate. The over-discharge resistance capability of the lithium ion battery made in the invention is excellent.
Description
Technical field
The present invention relates to a kind of lithium ion battery.
Background technology
Compare with other chemical power source, lithium ion battery has the performance of many excellences, as high in energy density, have extended cycle life, the advantage such as open circuit voltage is high, memory-less effect, safety non-pollution.Through the develop rapidly of recent two decades, lithium ion battery has been widely used in the fields such as mobile phone, notebook computer, digital camera.Along with the rise of global oil price and the enhancing of people's environmental consciousness, no matter be research institution or enterprise, all sight is concerned about in the exploitation of electric automobile.Researcher generally believes that lithium ion battery is a kind of most potential chemical power source being applied on electric automobile.Compare with other mobile device, electric automobile proposes higher requirement to performances such as the cycle life of battery, energy density, consistency of battery pack and large current discharging capabilities.
The battery pack of electric automobile is comprised of the connection in series-parallel of a large amount of monomer battery core, in battery pack, the consistency of monomer battery core is a huge test, because the self discharge of monomer battery core in battery pack can not be in full accord, cause between battery core SOC inconsistent, and then in battery power discharge or storing process, there is partial monosomy battery core can occur to put, it is brownout, in the time of the most dangerous, be to approach even to reach 0V, at this moment negative pole current potential conventionally can rise to and analyse copper current potential (about 3.5V), positive electrode potential also easily drops to the current potential (approximately-1V) that aluminium dissolves, after the copper of separating out or dissolving, the aluminium of reduction can puncture barrier film and cause serious internal short-circuit again, reduced the life-span of battery pack, also easily cause potential safety hazard.Also have thus the ubiquitous charged transportation problem of battery, nearly all battery is all charged transportation, also can bring safety problem, for lithium ion battery, even electric discharge transportation, its voltage is higher (if cobalt acid lithium battery discharge voltage is in 3.0V left and right) also, still with electric weight, if 0V is put to or approached to voltage, battery easily occurred to put, and caused short-circuit risks, as the accident such as get into an accident, can cause battery burning, even blast.
The focus of existing research particularly, lithium iron phosphate anode active material is for the battery of anodal preparation, because the discharge platform current potential of lithium iron phosphate anode active material is 3.45V left and right, this platform is very flat, almost can think a straight line that is parallel to X-axis, but arrived electric discharge end, its curve is almost an angle of 90 degrees straight glide, like this at discharge voltage below 2.0V the discharge voltage of the operated by rotary motion (limit), LiFePO4 has remained how many capacity hardly, be under identical discharging current condition, discharge time is very short, negative pole does not have lithium to deviate from substantially, to such an extent as to negative pole current potential is easy to rise to reach analyse copper current potential, thereby form copper dendrite, easily pierce through barrier film and cause battery short circuit, produce safety problem, LiFePO4 is put as the mistake of positive electrode active materials, the probability of short circuit is larger, even reached 100%.
In order to improve the security performance of lithium ion battery; the mistake that prevents lithium ion battery is put; avoid as far as possible charged transportation; in prior art, conventionally adopt protective circuit to be protected battery; but adopt the cost of protective circuit higher, and adopt protective circuit not delay or to stop battery core to cross to put potential safety hazard and the solution 0V voltage transportation problem occurring when approaching 0V.Therefore, need to find a kind of more suitable lithium ion battery that prevents and cross the technical scheme of putting.
Summary of the invention
The present invention is put the dissatisfactory technical problem of scheme in order to solve the anti-mistake of existing lithium ion battery, provides a kind of anti-mistake to put excellent performance and the good lithium ion battery of high-temperature behavior.
The object of this invention is to provide a kind of lithium ion battery, comprise housing and be sealed in electrode group and the electrolyte in housing, described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, described positive pole comprises anodal conducting base and is attached to the positive electrode material layer on anodal conducting base, and described positive electrode material layer comprises lithium iron phosphate anode active material, ferric phosphate, conductive agent and anodal binding agent; The smallest particles particle diameter of described ferric phosphate is not less than 20 microns; Described negative pole comprises negative pole conducting base and is attached to the negative electrode material layer on negative pole conducting base; Described negative electrode material layer comprises anode active material layer, and described anode active material layer comprises lithium and/or lithium alloy, negative active core-shell material and negative pole binding agent; Or described negative electrode material layer comprises anode active material layer and be attached to lithium and/or the lithium alloy in anode active material layer, described anode active material layer comprises negative active core-shell material and negative pole binding agent; Described negative active core-shell material comprises graphite and lithium titanate.
The present invention surprisingly finds the anti-exoergic power excellence of crossing of lithium ion battery itself prepared by the present invention, infer that reason may be because the polarization of oarse-grained ferric phosphate be large, difference of magnification, embedding lithium is slower, platform is lower, can delay positive electrode potential and decline, simultaneously, the rear lithium amount additionally providing is provided the lithium amount energy balance LiFePO4 that ferric phosphate returns embedding, prevents the copper dendrite that negative pole forms, in negative pole, contain lithium and/or lithium alloy, can in negative pole, embed in advance a certain amount of lithium, as extra lithium source, the lithium of pre-embedding can guarantee that after LiFePO4 electric discharge, continuing electric discharge still has lithium to deviate from from negative pole, prevent the rising of negative pole current potential, when particularly the present invention can solve battery cathode interpolation lithium or lithium alloy, easily generate Li dendrite, by the combination property with interaction energy raising battery of the present invention, the present invention can well apply lithium and/or lithium alloy in negative pole, not supplementing of conventional simple lithium, there will not be lithium and lithium alloy to embed in advance after negative pole irreversible, this part lithium can with positive pole of the present invention, negative pole interacts, can recycle, the cycle performance of battery is excellent, the anti-mistake of battery is put consistency of performance, in negative active core-shell material of the present invention, also contain lithium titanate simultaneously, at 1.5 ~ 1.8V, still have the platform of removal lithium embedded, can delay negative pole current potential rises, and LTO of the present invention makes voltage when 0V, positive electrode potential decline is few (can not cause aluminium to dissolve), the both positive and negative polarity of the battery that battery of the present invention can well be protected simultaneously, particularly in battery cathode of the present invention, can be good at applying lithium titanate material (LTO), the interaction of positive pole of the present invention and negative pole, make the high-temperature behavior of battery excellent, make can not consume electrolyte under LTO hot conditions, can not produce a large amount of gas, being not only LTO is well applied, and can not affect the performance of battery.After battery core prepared by the present invention is discharged to 2.0V, continue electric discharge and approach 0V, the anodal downward trend of potential curve and the ascendant trend of negative pole potential curve all tend towards stability and approach or intersect at 0V, only by the change of monomer battery core, be can realize battery prevented put, ensure the safety of monomer battery core, and can realize low-potential energy or uncharged transporting safely.
Accompanying drawing explanation
Fig. 1 is lithium ion battery three electrode charge and discharge voltage curves and the positive and negative reference potential curve (a is that cell voltage curve b is that positive pole-reference voltage curve c is negative pole-reference voltage curve) of the embodiment of the present invention 1 preparation.
Fig. 2 is the discharge voltage curve chart over time of the lithium ion battery of comparative example of the present invention 1 preparation.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The invention provides a kind of lithium ion battery, comprise housing and be sealed in electrode group and the electrolyte in housing, described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, described positive pole comprises anodal conducting base and is attached to the positive electrode material layer on anodal conducting base, and described positive electrode material layer comprises lithium iron phosphate anode active material, ferric phosphate, conductive agent and anodal binding agent; The smallest particles particle diameter of described ferric phosphate is not less than 20 microns; Described negative pole comprises negative pole conducting base and is attached to the negative electrode material layer on negative pole conducting base; Described negative electrode material layer comprises anode active material layer, and described anode active material layer comprises lithium and/or lithium alloy, negative active core-shell material and negative pole binding agent; Or described negative electrode material layer comprises anode active material layer and is attached to lithium and/or the lithium alloy in anode active material layer, described anode active material layer comprises negative active core-shell material and negative pole binding agent, now in anode active material layer, also can contain lithium and/or lithium alloy etc.; Described negative active core-shell material comprises graphite and lithium titanate.Lithium and/or lithium alloy can be to be configured to be coated in negative pole conducting base surface after cathode size together with negative active core-shell material, also can be on anode active material layer surface, to prepare one deck lithium and/or lithium alloy again after first applying conventional cathode size, can be also all to contain lithium and/or lithium alloy with anode active material layer surface in anode active material layer.Lithium iron phosphate anode active material of the present invention can be that the coated composite ferric lithium phosphate material of LiFePO4, carbon, the LiFePO4 of metal-doped modification etc. be take the positive electrode active materials that LiFePO4 is main body.
Further preferably, the particle primary particle size of ferric phosphate is 30 ~ 50 microns, primary particle median particle diameter D
50=35 ~ 45 microns.
Preferably, with respect to the lithium iron phosphate anode active material of 100 weight portions, the content of described ferric phosphate is 5-20 weight portion, more preferably 8-12 weight portion.
Preferably, with respect to the graphite of 100 weight portions, the content of described lithium titanate is 5-20 weight portion, more preferably 8 ~ 12 weight portions.
Preferably, the amount of lithium and/or lithium alloy meets k/L < x < (n-m)/L, wherein, x represents the quality of Li element in lithium and/or lithium alloy, L represents the theoretical specific capacity of lithium, m represents anodal initial charge capacity, and n represents the initial charge capacity of negative pole, and k represents the first charge-discharge irreversible capacity of negative pole.
With respect to the graphite of 100 weight portions, the content of described lithium and/or lithium alloy is 0.5 ~ 5 weight portion, more preferably 0.8-3 weight portion.
Preferably, lithium alloy is selected from one or more in Li-M alloy, and described M is selected from one or more in Be, Mg, Ti, Zr, V, Nb, Cr, Cu and Al.
Preferably, positive electrode also comprises carbon, and the specific area of described carbon is not less than 50m
2/ g, more preferably 200 ~ 600m
2/ g, utilizes the carbon of this special specific surface that capacity effect can occur in the application of lithium iron phosphate anode active material and delays positive electrode potential and decline; Carbon can adsorb lithium because of capacity effect, and the rear lithium additionally providing is provided the lithium amount energy balance LiFePO4 of its absorption, further improves the performance of battery.
Preferably, with respect to the lithium iron phosphate anode active material of 100 weight portions, the content of described carbon is 5-15 weight portion, more preferably 8-10 weight portion.
Preferably, positive electrode also comprises containing lithium additive, describedly containing lithium additive, is selected from Li
x1ni
y1mn
z1o
2, Li
x2m1
y2o
z2, silicate positive electrode active materials, Li
x3m2(WO
z3) in one or more, wherein, 0.8≤x1≤2,0≤y1 <, 1,0≤z1 < 1, 0.8≤x2≤7,0 < y2≤5,0 < z2≤8, 0.8≤x3≤7,2≤z3≤4, M1 is one or more in Fe, Co, Ni, Mn, Cu, Zn, Ti, V, Al or Mg, M2 is Fe, Co, Ni, Mn, Cu, Zn, Ti, V, one or more in Al or Mg, W is V, Mo, Ti, Nb, Zn, Sn, B, Y, one or more in Ge or As, preferably, lithium iron phosphate anode active material with respect to 100 weight portions, the described content containing lithium additive is not higher than 15 weight portions, further preferably, content containing lithium additive is 8-10 weight portion, it is the positive electrode active materials that is added with the special construction of a small amount of special ratios in lithium iron phosphate anode active material, the positive electrode active materials of this special construction is at initial charge rear section structure meeting inactivation, be equivalent to a certain amount of lithium of pre-embedding in negative pole, the lithium of the pre-embedding of this part still has lithium to deviate from from negative pole in the time of can guaranteeing to continue electric discharge after LiFePO4 electric discharge, simultaneously, Li
x2m1
y2o
z2and Li
x3m2(WO
z3) at 3.2V(LiFePO4 discharge platform) and below still have discharge platform, can also cushion the decline of positive electrode potential, and it not uses as the main positive electrode active materials of positive pole, but as additive, utilize the interaction of its structure and LiFePO4, can improve the performance of LiFePO4, and can not affect other performances of battery, can further improve the performance of battery.
Preferably, containing lithium additive, be selected from Li
0.95ni
0.84mn
0.21o
2, LiNi
0.5mn
0.5o
2, Li
2niO
2, Li
1.01ni
0.85mn
0.15o
2, Li
1.01ni
0.89mn
0.1o
2, Li
1.076ni
0.628mn
0.624o
2, Li
1.2ni
0.2mn
0.6o
2, Li
3feO
3, Li
5feO
4, Li
2mn
2o
4, Li
2mnO
3, Li
2cuO
2, Li
2feSiO
4, Li
2mnSiO
4, Li
2coSiO
4, Li
2niSiO
4, LiFeBO
3, Li
1.2niVO
4, LiFeMoO
4, LiCoTiO
4or LiMnSnO
4in one or more, further improve the performance of battery.
LiFePO4 the present invention is restriction not, improvements of the present invention are to interact by adding positive electrode active materials and the LiFePO4 of oarse-grained ferric phosphate, other special constructions, and match with the negative pole that contains ad hoc structure, be applied to battery, when battery charging and discharging, can prevent from putting, generally for various LiFePO4s, can realize the present invention, lithium iron phosphate anode active material can be purchased, the present invention is in order to improve the performance of battery, preferably, particle primary particle size is higher than 10 microns, more preferably 0.1 ~ 2 micron.
Electrolyte contains lithium salts and organic solvent, and preferably, lithium salts is selected from LiBF
4, Li
2b
12f
12, LiBOB, LiC
9h
3n
3f
3or LiNF
2s
2o
4in one or more, and do not adopt lithium hexafluoro phosphate, further improve the combination property of battery.
Wherein, organic solvent can be for gamma-butyrolacton, methyl ethyl carbonate, methyl propyl carbonate, dipropyl carbonate, acid anhydrides, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, N-methylacetamide, acetonitrile, DMF, sulfolane, methyl-sulfoxide, dimethyl sulfite and other is fluorine-containing, sulfur-bearing or containing one or more in the ring-type organic ester of unsaturated bond.The concentration of lithium salts in electrolyte can be 0.3-4 mol/L, is preferably 0.5-2 mol/L.
Preferably, the initial charge capacity of the initial charge capacity * coefficient of safety=graphite of lithium iron phosphate anode active material, the initial charge capacity of the capacity * coefficient of safety=lithium titanate of described lithium and/or lithium alloy, wherein, coefficient of safety is more than or equal to 0.8 and is less than or equal to 1.4.
Wherein, anodal conducting base is anodal conducting base known in those skilled in the art, for example, can be selected from aluminium foil, Copper Foil or various Punching steel strip.
Adhere to adopt and well known to a person skilled in the art various adherence methods, such as spraying, coating etc., generally can be coated on anodal conducting base by positive electrode being made after anode sizing agent to slurry etc. again.The anode sizing agent applying, except containing above-mentioned positive electrode of the present invention, generally comprises the solvent of dispersion use etc., also can contain other functional additives etc., in positive electrode, also can contain other functional additives.
Conductive agent, anodal binding agent and above-mentioned solvent etc. can be various material known in those skilled in the art, ratio the present invention of lithium iron phosphate anode active material, conductive agent, anodal binding agent and solvent etc. is also not particularly limited, can to material concentration, adjust flexibly according to the viscosity of the slurry coating of the composition of battery electrode positive electrode and positive electrode to be prepared and the requirement of operability, mode is conventionally known to one of skill in the art.
Improvements of the present invention are positive electrode, anodal preparation can adopt various technology well known in the art, for example, anode sizing agent is coated in to the surface of anodal conducting base, rear dry, calendering etc., wherein, dry, the step of calendering, like the prior art, dry conventionally under vacuum condition at 50-160 ℃, preferably carry out at 80-150 ℃, dry after dispersant in pole piece, can exist also and can not exist.Calendering can adopt the conventional rolling condition in this area, such as 0.5-3.0 MPa.Anodal preparation can also comprise other steps, for example, the cut-parts of reprocessing, cut-parts are known to the skilled person, and after having rolled, according to the anodal size of prepared battery request, cut, and obtain anode pole piece.
Negative pole conducting base can adopt in prior art the various negative pole conducting bases for lithium ion battery negative, as stamped metal, metal forming, net metal and foamed metal, and preferred Copper Foil.
The kind of negative pole binding agent and content are conventionally known to one of skill in the art, and for example fluorine resin and polyolefin compound are as one or more in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), butadiene-styrene rubber (SBR) and sodium carboxymethylcellulose (CMC); In general, according to the difference of binding agent kind used, with respect to the negative electrode active material of 100 weight portions, the content of negative pole binding agent is 0.005-8 weight portion, is preferably 0.008-5 weight portion.In cathode size, also can contain and strengthen the conductive agent of negative active core-shell material conductivity or other function additives etc.
The preparation of negative pole can be first by lithium and/or lithium alloy, negative active core-shell material and negative pole binding agent are configured to together slurry and are attached on negative pole conducting base, for example can be by lithium and/or lithium alloy, after negative active core-shell material and negative pole binding agent etc. are dry mixed, adopt the method for spraying to be attached on negative pole conducting base, also can be by lithium and/or lithium alloy, negative active core-shell material and negative pole binding agent etc. and solvent, selectivity is added after the wet mixings such as dispersant, adopt the methods such as slurry coating to be attached on negative pole conducting base, the general solvent now adopting is oil-based solvent, binding agent is oiliness binding agent.And then dry, calendering etc., wherein, dry, the step of calendering, like the prior art, dry conventionally under vacuum condition at 50-160 ℃, preferably carry out at 80-150 ℃, dry after dispersant in pole piece, can exist also and can not exist.Calendering can adopt the conventional rolling condition in this area, such as 0.5-3.0 MPa.The preparation of negative pole can also comprise other steps, for example, the cut-parts of reprocessing, cut-parts are known to the skilled person, and after having rolled, according to the negative pole size of prepared battery request, cut, and obtain cathode pole piece.
Also can be first negative active core-shell material and negative pole binding agent being configured to slurry is together attached on negative pole conducting base and prepares anode active material layer, adhere to adopt and well known to a person skilled in the art various adherence methods, such as spraying, coating etc., and then dry, calendering etc., wherein, dry, the step of calendering, like the prior art, at this, do not repeating.Can be in calendering, the lithium of predetermined amount and/or lithium alloy calendering is surperficial in anode active material layer, also can be after cutting, on the surface of negative plate, to lay lithium and/or the lithium alloy of one deck predetermined amount, and then calendering, at anode active material layer surface attachment one deck lithium and/or lithium alloy.The dew point that generally adds fashionable environment at lithium and/or lithium alloy is subzero below 50 ℃.
Wherein, barrier film can be selected from and well known to a person skilled in the art various barrier films used in lithium ion battery, for example polyolefin micro porous polyolefin membrane (PP), polyethylene felt (PE), glass mat or ultra-fine fibre glass paper or PP/PE/PP.As preferred embodiment a kind of, described barrier film is PP/PE/PP.
Housing the present invention is restriction not, can adopt and well known to a person skilled in the art various battery containers, and duricrusts such as box hat or aluminum hull, can be also the flexible package shells such as aluminum plastic film, and shape and large I design according to practical situation.
The preparation method of lithium ion battery provided by the invention can be well known for the person skilled in the art method, in general, the method comprises anodal, negative pole and the barrier film between positive pole and the negative pole formation pole piece of reeling successively, pole piece is inserted in battery case, add electrolyte, then sealing, wherein, the method for coiling and sealing is that those skilled in the art are known.The consumption of electrolyte is conventional amount used.
Unless stated otherwise, various solvent of the present invention and reagent are commercially available analytical reagent.
Below in conjunction with specific embodiment, the present invention is further described.
Embodiment 1
(1) anodal preparation:
By the LiFePO4 (D of 4 microns of the maximum primary particle particle diameters of 90g
50=0.3 micron), the ferric phosphate (D that the minimum primary particle particle diameter of 10g is 30 microns
50=35 microns), the binding agent Kynoar (PVDF) of 4g, the super conductive black of conductive agent SP(of 5g), the polyethylene of dispersing agent pyrrolidones (PVP) of 0.5g and the 1-METHYLPYRROLIDONE of 120g join in de-airing mixer and stir and form uniform anode sizing agent.This anode sizing agent is uniformly coated on to the both sides of the aluminium foil of 16 microns of thickness, then dries at 150 ℃.Again through roll-in, cut the positive plate that obtains size 453*40 millimeter.
(2) preparation of negative pole:
By 45g native graphite, 5g lithium titanate (LTO), 1g binding agent butadiene-styrene rubber breast (SBR), 0.5g binding agent carboxymethyl cellulose (CMC), 0.025g lithium metal powder (purity 99.9%), the NMP(N-methyl pyrrolidone of 125g) join in de-airing mixer and stir and form uniform cathode size.This cathode size is coated on to the both sides that thickness is the Copper Foil of 12 microns equably, then at 90 ℃, dries.Again through roll-in, cut, make the negative plate that is of a size of 455*41 millimeter.
(3) preparation of battery:
Respectively above-mentioned positive and negative electrode and polypropylene screen are wound into the pole piece of a square lithium ion battery, subsequently by LiBF
4by the concentration of 1 mol/L, be dissolved in the mixed solvent of EC/EMC/DEC=1:1:1 and form nonaqueous electrolytic solution, this electrolyte is injected to battery aluminum shell with the amount of 3.8g/Ah, sealing, changes into, and makes lithium ion battery.
Adopt the method identical with embodiment 1 and step preparation positive pole, negative pole and battery, different is the configuration of anode sizing agent: by the LiFePO4 of 93g (primary particle particle diameter D
50=0.4 micron), ferric phosphate (the primary particle particle diameter D that the minimum grain size of 7g is 30 microns
50=45 microns), the binding agent Kynoar (PVDF) of 4g, the super conductive black of conductive agent SP(of 5g), the polyethylene of dispersing agent pyrrolidones (PVP) of 0.5g and the 1-METHYLPYRROLIDONE of 120g join in de-airing mixer and stir and form uniform anode sizing agent.The preparation of negative pole: by 45g native graphite, 5g LTO, 1g binding agent butadiene-styrene rubber breast (SBR), 0.5g binding agent carboxymethyl cellulose (CMC), the deionized water of 125g joins in de-airing mixer and stirs and form uniform cathode size.This cathode size is coated on to the both sides that thickness is the Copper Foil of 12 microns equably, then at 90 ℃, dries.Again through roll-in, cut, makes the negative plate that is of a size of 455*41 millimeter, then the lithium-aluminium alloy powder of 0.025 gram (aluminium content 3 % by weight) is sprayed on to anode active material layer surface, then roll-in makes negative plate.The lithium salts of the electrolyte injecting is Li
2b
12f
12.
Adopt the method identical with embodiment 1 and step preparation positive pole, negative pole and battery, different is the configuration of cathode size: by 45g native graphite, 5g LTO, 1g binding agent butadiene-styrene rubber breast (SBR), 0.5g binding agent carboxymethyl cellulose (CMC), 0.016g lithium metal powder (purity 99.9%), the NMP of 125g joins in de-airing mixer and stirs and form uniform cathode size.
Adopt the method identical with embodiment 1 and step preparation positive pole, negative pole and battery, different is the configuration of anode sizing agent: by the LiFePO4 of 90g, and the ferric phosphate that the minimum grain size of 10g is 30 microns (primary particle particle diameter D
50=25 microns), the binding agent Kynoar (PVDF) of 4g, the super conductive black of conductive agent SP(of 5g), the polyethylene of dispersing agent pyrrolidones (PVP) of 0.5g and the 1-METHYLPYRROLIDONE of 120g join in de-airing mixer and stir and form uniform anode sizing agent.
Embodiment 5
Adopt the method identical with embodiment 1 and step preparation positive pole, negative pole and battery, different is the configuration of anode sizing agent: by the LiFePO4 of 90g, and the ferric phosphate that the minimum grain size of 10g is 30 microns (primary particle particle diameter D
50=50 microns), the binding agent Kynoar (PVDF) of 4g, the super conductive black of conductive agent SP(of 5g), the polyethylene of dispersing agent pyrrolidones (PVP) of 0.5g and the 1-METHYLPYRROLIDONE of 120g join in de-airing mixer and stir and form uniform anode sizing agent.
Embodiment 6
Adopt the method identical with embodiment 1 and step preparation positive pole, negative pole and battery, different is the configuration of anode sizing agent: by the LiFePO4 of 90g, and the ferric phosphate that the minimum grain size of 7g is 30 microns (primary particle particle diameter D
50=45 microns), the binding agent Kynoar (PVDF) of 4g, the super conductive black of conductive agent SP(of 5g), the polyethylene of dispersing agent pyrrolidones (PVP) of 0.5g and the 1-METHYLPYRROLIDONE of 120g join in de-airing mixer and stir and form uniform anode sizing agent.
Embodiment 7
Adopt the method identical with embodiment 1 and step preparation positive pole, negative pole and battery, different is the configuration of anode sizing agent: by 90g LiFePO4, the minimum grain size of 7 grams is the ferric phosphate of 30 microns, and 5 grams of specific areas are 120m
2the material with carbon element of/g, 4g Kynoar (PVDF), the conductive agent SP of 5g, the polyethylene of dispersing agent pyrrolidones (PVP) of 0.5g and the 1-METHYLPYRROLIDONE of 120g join in de-airing mixer and stir and form uniform anode sizing agent.
Embodiment 8
Adopt the method identical with embodiment 1 and step preparation positive pole, negative pole and battery, different is the configuration of anode sizing agent: by 90g LiFePO4, the minimum grain size of 7 grams is the ferric phosphate of 30 microns, and 7 grams of specific areas are 1200m
2the material with carbon element of/g, 4g Kynoar (PVDF), the conductive agent SP of 5g, the polyethylene of dispersing agent pyrrolidones (PVP) of 0.5g and the 1-METHYLPYRROLIDONE of 120g join in de-airing mixer and stir and form uniform anode sizing agent.
Embodiment 9
Adopt the method identical with embodiment 1 and step preparation positive pole, negative pole and battery, different is the configuration of anode sizing agent: by 90g LiFePO4, the minimum grain size of 7 grams is the ferric phosphate of 30 microns, and 8 grams of specific areas are 1000m
2the material with carbon element of/g, 4g Kynoar (PVDF), the conductive agent SP of 5g, the polyethylene of dispersing agent pyrrolidones (PVP) of 0.5g and the 1-METHYLPYRROLIDONE of 120g join in de-airing mixer and stir and form uniform anode sizing agent.
Embodiment 10
Adopt the method identical with embodiment 1 and step preparation positive pole, negative pole and battery, different is the configuration of anode sizing agent: adopt the method identical with embodiment 1 and step preparation positive pole, negative pole and battery, different is the configuration of anode sizing agent: by 90g LiFePO4, and the Li of 5g
2mnSiO
4, 3 grams of Li
5feO
4the minimum grain size of 7 grams is the ferric phosphate of 30 microns, 4g Kynoar (PVDF), the conductive agent SP of 5g, the polyethylene of dispersing agent pyrrolidones (PVP) of 0.5g and the 1-METHYLPYRROLIDONE of 120g join in de-airing mixer and stir and form uniform anode sizing agent.
The configuration of cathode size: by 45g native graphite, the lithium titanate of 5g, 1g binding agent butadiene-styrene rubber breast (SBR), 0.5g binding agent carboxymethyl cellulose (CMC), 0.016g lithium metal powder (purity 99.9%), the NMP of 125g joins in de-airing mixer and stirs and form uniform cathode size.
The lithium salts of the electrolyte injecting is LiNF
2s
2o
4.
Comparative example 1
(1) anodal preparation:
By 100g LiFePO4,4g Kynoar (PVDF), 5g conductive agent SP, 0.5g polyethylene of dispersing agent pyrrolidones (PVP), the 1-METHYLPYRROLIDONE of 120g joins in de-airing mixer and stirs and form uniform positive electrode.This positive electrode is uniformly coated on to the both sides of the aluminium foil of 20 microns of thickness, then dries at 150 ℃.Again through roll-in, cut the positive plate that obtains size 453*40 millimeter.
(2) preparation of negative pole:
By 50g native graphite, 1g binding agent butadiene-styrene rubber breast (SBR), 0.5g binding agent carboxymethyl cellulose (CMC), the NMP of 125g joins in de-airing mixer and stirs and form uniform cathode size.This cathode size is coated on to the both sides that thickness is the Copper Foil of 12 microns equably, then at 90 ℃, dries.Again through roll-in, cut, make the negative plate that is of a size of 455*41 millimeter.
(3) preparation of battery:
Respectively above-mentioned positive and negative electrode and polypropylene screen are wound into the pole piece of a square lithium ion battery, subsequently by LiPF
6by the concentration of 1 mol/L, be dissolved in the mixed solvent of EC/EMC/DEC=1:1:1 and form nonaqueous electrolytic solution, this electrolyte is injected to battery aluminum shell with the amount of 3.8g/Ah, sealing, changes into, and makes lithium ion battery.
Comparative example 2
Adopt the method identical with comparative example 1 and step preparation positive pole, negative pole and battery, different is the configuration of cathode size: by 45g native graphite, 5g lithium titanate (LTO), 1g binding agent butadiene-styrene rubber breast (SBR), 0.5g binding agent carboxymethyl cellulose (CMC), the NMP of 125g joins in de-airing mixer and stirs and form uniform cathode size.
Electrochemical property test:
Battery prepared by embodiment 1-10 and comparative example 1-2 is placed on the type electrochemical property test instrument of new Weir-3000, charges to 3.6V respectively with 0.1C, shelve 10 minutes, after with 0.1C, be discharged to 2.0V.Then this battery is prepared into three electrodes, with 0.5C, charges to 3.6V, shelve 10 minutes, after with 0.5C, be discharged to 2.0V, uninterrupted, then continue to discharge into 0V with 0.5C.Record battery in discharge capacity and the discharge capacity of battery when 2.0V is above of 2.0-0V, the ratio value of the discharge capacity by battery when the shared 2.0V of the discharge capacity under 2.0-0V is above is recorded in table 1.Meanwhile, when battery discharge is arrived to 0V, the potential value of battery cathode is recorded in table 1.Curve is as Fig. 1 over time for the three-electrode voltage that embodiment 1 draws, and comparative example 1 is drawn voltage curve chart over time, as Fig. 2.
Battery prepared by embodiment 1 and comparative example 1-2 is placed on the type electrochemical property test instrument of new Weir-3000, with 0.1C, charge to 4.3V(embodiment 1 respectively) or 3.6V(comparative example 1-2), shelve 10 minutes, after with 0.1C, be discharged to 2.0V, then with 0.2C circulation 3 times, record average size; Be full of again electricity, be placed in 85 ℃ of baking boxs and deposit 2 days, take out afterwards electric discharge, record discharge capacity, as residual capacity, calculated capacity surplus ratio=(residual capacity/average size * 100%); Again with 0.2C, be full of electricity and discharge again, record discharge capacity, as recovery capacity, capacity restoration rate=(recovery capacity/average size * 100%), test result is in Table 1.
Table 1
| Embodiment | Discharge capacity more than discharge capacity/2.0V of 2.0V ~ 0V (%) | Battery discharge is during to 0V, the current potential of battery cathode (V) | Capacity surplus ratio % | Capacity restoration rate % |
| Embodiment 1 | 14 | 1.67 | 93% | 94 |
| Embodiment | ||||
| 2 | 11 | 1.66 | / | / |
| |
9 | 1.68 | / | / |
| |
11 | 1.66 | / | / |
| Embodiment 5 | 21 | 1.67 | / | / |
| Embodiment 6 | 19 | 1.65 | / | / |
| Embodiment 7 | 16 | 1.65 | / | / |
| Embodiment 8 | 28 | 1.63 | / | / |
| Embodiment 9 | 19 | 1.65 | / | / |
| Embodiment 10 | 14 | 1.68 | / | / |
| Comparative example 1 | 0.8 | 2.4 | 91% | 92% |
| Comparative example 2 | 8 | 1.55 | 76% | 78% |
By data in table 1, can be found out, the discharge capacity of the battery of embodiment 1-10 under 2.0-0V condition be the discharge capacity under the above condition of 2.0V with respect to battery, proportion is higher, and the capacity that comparative example 1,2 can be emitted under 2.0-0V condition is low-down, put under condition can stable negative electrode potential crossing for the battery that embodiment 1-10 is described, make negative pole current potential be unlikely to be raised to fast and analyse copper current potential, cause short circuit, thereby play the effect that prevents or delayed to put, battery is significantly improved in the security performance under condition to one's heart's content; The high-temperature behavior of battery prepared by the present invention is simultaneously excellent, can access good application.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (16)
1. a lithium ion battery, is characterized in that, comprises housing and is sealed in electrode group and the electrolyte in housing, and described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole,
Described positive pole comprises anodal conducting base and is attached to the positive electrode material layer on anodal conducting base, and described positive electrode material layer comprises lithium iron phosphate anode active material, ferric phosphate, conductive agent and anodal binding agent; The particle primary particle size of described ferric phosphate is not less than 20 microns;
Described negative pole comprises negative pole conducting base and is attached to the negative electrode material layer on negative pole conducting base;
Described negative electrode material layer comprises anode active material layer, and described anode active material layer comprises lithium and/or lithium alloy, negative active core-shell material and negative pole binding agent;
Or described negative electrode material layer comprises anode active material layer and be attached to lithium and/or the lithium alloy in anode active material layer, described anode active material layer comprises negative active core-shell material and negative pole binding agent;
Described negative active core-shell material comprises graphite and lithium titanate.
2. lithium ion battery according to claim 1, is characterized in that, the particle primary particle size of described ferric phosphate is 30 ~ 50 microns, primary particle median particle diameter D
50=35 ~ 45 microns.
3. lithium ion battery according to claim 1, is characterized in that, with respect to the lithium iron phosphate anode active material of 100 weight portions, the content of described ferric phosphate is 5-20 weight portion.
4. lithium ion battery according to claim 3, is characterized in that, with respect to the lithium iron phosphate anode active material of 100 weight portions, the content of described ferric phosphate is 8-12 weight portion.
5. lithium ion battery according to claim 1, is characterized in that, with respect to the graphite of 100 weight portions, the content of described lithium titanate is 5-20 weight portion.
6. lithium ion battery according to claim 5, is characterized in that, with respect to the graphite of 100 weight portions, the content of described lithium titanate is 8-12 weight portion.
7. lithium ion battery according to claim 1, it is characterized in that, the amount of described lithium and/or lithium alloy meets k/L < x < (n-m)/L, wherein, x represents the quality of Li element in lithium and/or lithium alloy, and L represents the theoretical specific capacity of lithium, and m represents anodal initial charge capacity, n represents the initial charge capacity of negative pole, and k represents the first charge-discharge irreversible capacity of negative pole.
8. lithium ion battery according to claim 1, is characterized in that, with respect to the graphite of 100 weight portions, the content of described lithium and/or lithium alloy is 0.5 ~ 5 weight portion.
9. lithium ion battery according to claim 1, is characterized in that, described lithium alloy is selected from one or more in Li-M alloy, and described M is selected from one or more in Be, Mg, Ti, Zr, V, Nb, Cr, Cu and Al.
10. lithium ion battery according to claim 1, is characterized in that, described positive electrode also comprises carbon, and the specific area of described carbon is not less than 50m
2/ g.
11. lithium ion batteries according to claim 10, is characterized in that, with respect to the lithium iron phosphate anode active material of 100 weight portions, the content of described carbon is 5-15 weight portion; The specific area of described carbon is 200 ~ 600m
2/ g.
12. lithium ion batteries according to claim 1, is characterized in that, described positive electrode also comprises containing lithium additive, describedly containing lithium additive, are selected from Li
x1ni
y1mn
z1o
2, Li
x2m1
y2o
z2, silicate positive electrode active materials or Li
x3m2(WO
z3) in one or more, wherein, 0.8≤x1≤2,0≤y1 <, 1,0≤z1 < 1; 0.8≤x2≤7,0 < y2≤5,0 < z2≤8; 0.8≤x3≤7,2≤z3≤4; M1 is one or more in Fe, Co, Ni, Mn, Cu, Zn, Ti, V, Al or Mg; M2 is one or more in Fe, Co, Ni, Mn, Cu, Zn, Ti, V, Al or Mg, and W is one or more in V, Mo, Ti, Nb, Zn, Sn, B, Y, Ge or As; With respect to the lithium iron phosphate anode active material of 100 weight portions, the described content containing lithium additive is not higher than 15 weight portions.
13. lithium ion batteries according to claim 12, is characterized in that, the described lithium additive that contains is selected from Li
0.95ni
0.84mn
0.21o
2, LiNi
0.5mn
0.5o
2, Li
2niO
2, Li
1.01ni
0.85mn
0.15o
2, Li
1.01ni
0.89mn
0.1o
2, Li
1.076ni
0.628mn
0.624o
2, Li
1.2ni
0.2mn
0.6o
2, Li
3feO
3, Li
5feO
4, Li
2mn
2o
4, Li
2mnO
3, Li
2cuO
2, Li
2feSiO
4, Li
2mnSiO
4, Li
2coSiO
4, Li
2niSiO
4, LiFeBO
3, Li
1.2niVO
4, LiFeMoO
4, LiCoTiO
4or LiMnSnO
4in one or more.
14. lithium ion batteries according to claim 1, is characterized in that, the particle primary particle size of described lithium iron phosphate anode active material is not higher than 10 microns.
15. lithium ion batteries according to claim 1, is characterized in that, described electrolyte comprises lithium salts and organic solvent, and described lithium salts is selected from LiBF
4, Li
2b
12f
12, LiBOB, LiC
9h
3n
3f
3or LiNF
2s
2o
4in one or more.
16. lithium ion batteries according to claim 1, it is characterized in that, the initial charge capacity of the initial charge capacity * coefficient of safety=graphite of described lithium iron phosphate anode active material, the initial charge capacity of the capacity * coefficient of safety=lithium titanate of described lithium and/or lithium alloy, wherein, coefficient of safety is more than or equal to 0.8 and is less than or equal to 1.4.
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| CN107240716A (en) * | 2016-03-28 | 2017-10-10 | 比亚迪股份有限公司 | A kind of electrolyte, positive pole and preparation method thereof and a kind of lithium ion battery |
| CN109994769A (en) * | 2017-12-30 | 2019-07-09 | 程艳青 | A kind of large-capacity high-power start and stop ferric phosphate lithium cell manufacturing method |
| CN112652761A (en) * | 2020-12-02 | 2021-04-13 | 珠海格力电器股份有限公司 | Ternary lithium ion battery capable of discharging to 0V and preparation method thereof |
| CN115312701A (en) * | 2022-09-29 | 2022-11-08 | 比亚迪股份有限公司 | Positive plate and lithium ion battery |
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| CN102640332A (en) * | 2010-09-27 | 2012-08-15 | 松下电器产业株式会社 | Positive electrode active material particles for lithium ion secondary battery, positive electrode using said positive electrode active material particles, and lithium ion secondary battery |
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| US20070059602A1 (en) * | 2005-09-15 | 2007-03-15 | Hideaki Morishima | Nonaqueous electrolyte battery and battery pack |
| CN102640332A (en) * | 2010-09-27 | 2012-08-15 | 松下电器产业株式会社 | Positive electrode active material particles for lithium ion secondary battery, positive electrode using said positive electrode active material particles, and lithium ion secondary battery |
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| CN107240716A (en) * | 2016-03-28 | 2017-10-10 | 比亚迪股份有限公司 | A kind of electrolyte, positive pole and preparation method thereof and a kind of lithium ion battery |
| CN107240716B (en) * | 2016-03-28 | 2019-12-20 | 比亚迪股份有限公司 | Electrolyte, positive electrode and preparation method thereof, and lithium ion battery |
| CN109994769A (en) * | 2017-12-30 | 2019-07-09 | 程艳青 | A kind of large-capacity high-power start and stop ferric phosphate lithium cell manufacturing method |
| CN112652761A (en) * | 2020-12-02 | 2021-04-13 | 珠海格力电器股份有限公司 | Ternary lithium ion battery capable of discharging to 0V and preparation method thereof |
| CN115312701A (en) * | 2022-09-29 | 2022-11-08 | 比亚迪股份有限公司 | Positive plate and lithium ion battery |
| CN115312701B (en) * | 2022-09-29 | 2023-02-10 | 比亚迪股份有限公司 | Positive plate and lithium ion battery |
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