CN101425580A - Negative electrode active substance of lithium ionic cell and preparing method thereof, negative electrode and cell - Google Patents
Negative electrode active substance of lithium ionic cell and preparing method thereof, negative electrode and cell Download PDFInfo
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- CN101425580A CN101425580A CNA2007101654760A CN200710165476A CN101425580A CN 101425580 A CN101425580 A CN 101425580A CN A2007101654760 A CNA2007101654760 A CN A2007101654760A CN 200710165476 A CN200710165476 A CN 200710165476A CN 101425580 A CN101425580 A CN 101425580A
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Abstract
The invention relates to a cathode active substance of a lithium ion battery. The cathode active substance contains carbon material and metal oxide; the metal oxide is clad on the surface of the carbon material and adopts one or some of s IIA, IIIA, IB, IB, IIIB and IVB metal oxides in an element periodic table. The battery prepared and obtained by the cathode active substance has good safe performance and electrical chemical property.
Description
Technical field
The invention relates to a kind of battery cathode active substance and preparation method thereof and negative pole and battery, more specifically say so about a kind of lithium ion battery negative pole active materials and preparation method thereof and negative pole and battery.
Background technology
The battery of lithium rechargeable battery mainly comprises positive plate, barrier film and negative plate, the barrier film between positive plate and negative plate wherein, mainly play the positive and negative electrode of isolating battery, prevent the two poles of the earth contact and the effect of short circuit makes electrolyte ion come in and go out freely simultaneously.At present, the barrier film in the lithium rechargeable battery is mainly made by the micro-porous film that polyolefin-based resins such as polyethylene, polypropylene are formed, and at high temperature shrinks easily.If battery generation internal short-circuit or sharp objects is arranged such as acupuncture penetrates it may shrink because of the reaction heat that moment is short-circuited, enlarge the short circuit part.The expansion of short circuit part like this can further produce a large amount of reaction heat, impels the overheated unusually of battery.Also have, when battery places high temperature occasion more than 150 ℃, micro-porous film can produce and shrink or fusion, produces distortion in (on the especially convoluted pole plate group) on the pole plate group, be short-circuited between both positive and negative polarity, battery also may therefore be absorbed in unusual overheated in.
Therefore, fail safe in order to ensure lithium rechargeable battery, usually adopt battery diaphragm is carried out improved method, but all deposit defective in various degree separately, a kind of barrier film that is used for high power lithium ion cell is disclosed as CN1679185A, this barrier film is based on the flexible sheet form matrix, described matrix has many openings, and on the described matrix and matrix in have porous inorganic electric insulation coating layer, this coating makes the closure of openings of matrix, the material of described matrix is selected from nonconducting non-woven polymer fiber, and described inorganic electric insulation coating layer comprises particle, described barrier film is characterised in that, this barrier film need not electrolyte and exists and promptly have the lithium ion conducting performance and be electrical insulator.The particle of described inorganic electric insulation coating layer comprises the oxide particle of element al, Zr and/or Si.
By avoiding to a certain extent to the improvement of described barrier film because micro-porous film produces the safety problem of the battery that thermal contraction or fusion cause, but because inorganic coating has certain fragility, the part barrier film that particularly tortuosity is bigger when reeling is difficult to folding line, damaged particle detachment down to inorganic coating can take place with avoiding, thereby battery is caused potential safety hazard.And in the process of processing battery, barrier film is offset easily, and internal short-circuit easily takes place.In addition, another problem that this barrier film faced is that the thickness of barrier film is difficult to reduce, and thicker barrier film can reduce the volume of battery capacity, does not meet the application requirements of high-capacity battery.
And for example CN1523687A discloses a kind of lithium rechargeable battery, it is to have positive pole, negative pole, dividing plate between positive pole and negative pole and lithium salts is dissolved in the lithium rechargeable battery of the electrolyte in the nonaqueous solvents, wherein, aforementioned separator plate is made of the porous rete that contains alkali solid particulate and composite adhesive, aforementioned porous rete is engaged with at least one side's the surface of aforementioned positive pole and aforementioned negative pole, aforementioned composite adhesive is made of primary binder and secondary adhesive, aforementioned primary binder is made of polyether sulfone, and the aforementioned auxiliary adhesive is made of polyvinylpyrrolidone.The alkali solid particulate that contains in the described formation dividing plate contains Alpha-alumina at least.
This rete is attached to the surface of negative or positive electrode, but because the porous rete is a kind of inorganic compounding layer, the ability that circumnutates is relatively poor, therefore, easily folding is broken in follow-up winding process described inorganic compounding layer too, especially in initial volume around broken problem easy to break of bigger stage of tortuosity.Therefore, this membrane layer can not really prevent the problem of battery generation internal short-circuit equally effectively.Simultaneously, this inorganic compounding layer can not stop the deterioration of inside battery reaction when over-charging of battery, thereby makes the over-charging variation of battery.
Summary of the invention
The objective of the invention is to overcome the relatively poor defective of security performance of the lithium ion battery of prior art, provide a kind of make battery have good safety can lithium ion battery negative pole active materials and preparation method thereof and negative pole and battery.
The present inventor finds, in the prior art, in order to improve and guarantee the security performance of lithium rechargeable battery, usually adopt battery diaphragm is carried out improved method, and it is also not fully up to expectations to the improvement of battery diaphragm to the improvement of lithium rechargeable battery security performance, and, also can bring some negative effects to the chemical property of battery, and the present inventor is under the prerequisite of the battery diaphragm that uses this area routine, improvement by the anticathode active material, make battery security performance be improved significantly, and battery has excellent cycle performance simultaneously.
The invention provides a kind of lithium ion battery negative pole active materials, wherein, this negative electrode active material contains material with carbon element and metal oxide, described metal oxide is coated on the surface of material with carbon element, and described metal oxide is selected from one or more in the oxide of IIA in the periodic table of elements, IIIA, IB, IIB, IIIB and IVB family metal.
The present invention also provides a kind of preparation method of lithium ion battery negative pole active materials, wherein, this method comprises material with carbon element, soluble metallic salt and solvent, dry then, and at 400-500 ℃ of following sintering, described soluble metallic salt is selected from one or more in the soluble metallic salt of IIA in the periodic table of elements, IIIA, IB, IIB, IIIB and IVB family metal.
The present invention also provides a kind of negative pole of lithium ion battery, this negative pole comprises collector body and the negative material that loads on this collector body, described negative material contains negative electrode active material and adhesive, and wherein, described negative electrode active material is a negative electrode active material provided by the invention.
A kind of lithium ion battery, this battery comprises pole piece and nonaqueous electrolytic solution, and described pole piece and nonaqueous electrolytic solution are sealed in the battery container, and described pole piece comprises positive pole, negative pole and barrier film, and wherein, described negative pole is a negative pole provided by the invention.
Negative electrode active material of the present invention contains material with carbon element and metal oxide, described metal oxide is coated on the surface of material with carbon element, the described metal oxide that is coated on carbon material surface has good ionic conductivity and weak electron conduction, therefore, can not hinder the normal contact of lithium ion between both positive and negative polarity, but, in case situations such as battery generation internal short-circuit, the coating layer of the metal oxide of carbon material surface can play the effect of isolating negative material and positive electrode, and can play the effect of certain prevention thermal diffusion, thereby effectively improved the security performance of battery.
In addition, the metal oxide that carbon material surface coats can effectively suppress the material with carbon element in the removal lithium embedded process, as the change of graphite-structure, has guaranteed its stability of structure, and this has certain effect to the improvement of material with carbon element cycle performance and the control of cell thickness.And the described metal oxide that evenly is coated on carbon material surface also has electrolyte and well soaks and absorbability, thereby has driven the abundant infiltration of electrolyte between whole negative active core-shell material.This to form at carbon material surface evenly, stable SEI film is very favorable, also helping lithium ion freely embeds in material with carbon element and deviates from, reduce the risk that causes breakage of SEI film and generation Li dendrite because of local insufficient electrolyte, thereby further improved the security performance and the cycle performance of battery.
Embodiment
According to the present invention, described negative electrode active material contains material with carbon element and metal oxide, described metal oxide is coated on the surface of material with carbon element, described metal oxide is selected from one or more in the oxide of IIA in the periodic table of elements, IIIA, IB, IIB, IIIB and IVB family metal, and described metal oxide is preferably selected from MgO, Al
2O
3, CuO, ZnO, TiO
2, BaO and ZrO
2In one or more.
Al
2O
3Belong to the strongly hydrophilic material, the contact angle of it and water is 0 °, and conventional material with carbon element such as graphite are lyophobic dusts, and the contact angle of it and water is between 40 °-90 °.According to wetting principle (polarity principle of similarity), particle is easy more wetting by liquid, and resulting suspension is stable more, and particle is got over not free settling.Therefore, in the water-based batching system of negative electrode active material, the surface has coated Al
2O
3The material with carbon element and the wetability of water better, the cathode size for preparing is more stable, thus the stability of pulling phase when can more effective assurance preparing negative pole makes the consistency of the cathode pole piece that makes and lithium ion battery better.Therefore, more preferably under the situation, described metal oxide is Al
2O
3
Material with carbon element in the described negative electrode active material is not particularly limited with the weight ratio that is coated on the metal oxide of carbon material surface, for the material with carbon element after guaranteeing to coat has good electrical conductivity, and can guarantee that again described metal oxide can evenly be coated on the surface of material with carbon element, under the preferable case, total amount with described negative electrode active material is a benchmark, the content of described material with carbon element is 97.0-99.9 weight %, more preferably 98.0-99.8 weight %; The content of described metal oxide is 0.1-3.0 weight %, more preferably 0.2-2.0 weight %.
The kind of described material with carbon element is conventionally known to one of skill in the art, can be the various material with carbon elements that disengage lithium that embed of this area routine, such as in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules and the carbon fiber one or more, be preferably in Delanium, petroleum coke and the carbonaceous mesophase spherules one or more.
According to the present invention, the preparation method of described lithium ion battery negative pole active materials, promptly, the method that makes metal oxide be coated on the surface of material with carbon element can adopt the method for coating of the various routines in this area, as, described method comprises material with carbon element, soluble metallic salt and solvent, and is dry then, and at 400-500 ℃ of following sintering.After with material with carbon element, soluble metallic salt and solvent, soluble metallic salt dissolves, and is immersed in the surface of material with carbon element, and in sintering process subsequently, soluble metallic salt at high temperature is decomposed to form metal oxide and is coated on the surface of material with carbon element then.According to the present invention, described soluble metallic salt is selected from one or more in the soluble metallic salt of IIA in the periodic table of elements, IIIA, IB, IIB, IIIB and IVB family metal, for example, and the nitrate Mg (NO of soluble metal
3)
2, Al (NO
3)
3, Cu (NO
3)
2, Zn (NO
3)
2, Ti (NO
3)
4, Ba (NO
3)
2, Zr (NO
3)
4Deng, under the preferable case, described soluble metallic salt is selected from Al (NO
3)
3, Mg (NO
3)
2, Zn (NO
3)
2, Cu (NO
3)
2And Ba (NO
3)
2In one or more.
The ratio of described soluble metallic salt and material with carbon element is not particularly limited, under the preferable case, the consumption of described soluble metallic salt makes in the negative electrode active material that obtains, the content of metal oxide and material with carbon element is respectively the 0.1-3.0 weight % of the total amount of negative electrode active material, be preferably 0.2-2.0 weight % and 97.0-99.9 weight %, be preferably 98.0-99.8 weight %.
For the material with carbon element after guaranteeing to coat has good electrical conductivity, and can guarantee that again described metal oxide can evenly be coated on the surface of material with carbon element, the soluble metallic salt in the described soluble metal salting liquid and the weight ratio of material with carbon element are preferably 0.4-10:100, more preferably 0.8-7.0:100.
The effect of described solvent is to make the soluble metallic salt dissolving, forms the soluble metal salting liquid, and mixes with material with carbon element, makes in the described soluble metal salting liquid of being dispersed in of material with carbon element homogeneous and forms homogeneous, steady suspension.Therefore, described solvent types and consumption are not particularly limited, be preferably the soluble metal salt solubility greatly is easy to any solvent of volatilizing again, and can be inorganic solvent such as water, also can be organic solvent, as absolute ethyl alcohol (alcohol), ethylene glycol, ether, acetone etc.Because organic solvent is difficult for making material with carbon element to reunite in the process of oven dry, and easily oven dry, so the preferred solvent of the present invention is an alcohol.
The method of described drying and condition are conventionally known to one of skill in the art, can be room temperature to 150 ℃ as the temperature of drying, and the dry time can be 10-24 hour.
Some soluble metallic salts such as Al (NO
3)
3Be easy to suction, often with Al (NO
3)
39H
2The form of O exists, and therefore, preferably before with described soluble metallic salt and material with carbon element and solvent, carries out drying earlier.
The method of described sintering can adopt and well known to a person skilled in the art sintering method, and the condition of sintering comprises the temperature of sintering and the time of sintering, and the temperature of described sintering is the decomposition temperature that is higher than soluble metallic salt, as Al (NO
3)
3Decomposition temperature about 160 ℃, therefore, sintering temperature need be more than 160 ℃; consider material with carbon element simultaneously; as graphite under the temperature more than 600 ℃ in air meeting and oxygen reaction, therefore, under condition of overhigh temperature; must adopt inert gas; carry out atmosphere protection as nitrogen or zero group gas such as helium, consider that from the angle of saving cost the temperature of described sintering generally will be lower than 600 ℃; be generally 400-500 ℃, the time of sintering is generally 2-6 hour.
According to the negative pole of lithium ion battery provided by the invention, this negative pole comprises collector body and the negative material that loads on this collector body, and described negative material contains negative electrode active material and adhesive, and described negative electrode active material is a negative electrode active material provided by the invention.
The kind of described negative pole adhesive and content are conventionally known to one of skill in the art, for example one or more in fluorine resin and polyolefin compound such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) and butadiene-styrene rubber (SBR) and the polyvinyl alcohol.In general, according to the difference of used negative pole adhesive kind, be benchmark with the weight of negative electrode active material, the content of negative pole adhesive is 0.5-8 weight %, is preferably 1-5 weight %.
Negative pole of the present invention can also and preferably contain conductive agent, be coated with the conductivity of the material with carbon element of metal oxide with further raising, described conductive agent is not particularly limited, can be the cathode conductive agent of this area routine, such as in acetylene black, conductive carbon black and electrically conductive graphite, microparticle graphite, the carbon fiber one or more, be preferably microparticle graphite, the particle diameter of described microparticle graphite is generally the 0.5-6 micron.Weight with negative electrode active material is benchmark, and the content of described conductive agent is 0.1-5 weight %, is preferably 0.2-3 weight %.
Negative electrode collector can be for negative electrode collector conventional in the lithium ion battery, as stamped metal, and metal forming, net metal, foamed metal uses Copper Foil as negative electrode collector in specific embodiments of the present invention.
The preparation method of described negative pole comprises that the slurry that will contain negative electrode active material and negative pole adhesive and solvent applies and/or is filled on the collector body, drying, and calendering, wherein, described adhesive is the enol based polyalcohol.Wherein, described solvent can be selected from one or more in N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols.The consumption of described solvent can make described pastel have viscosity and flowability, can be coated on the described collector body to get final product.In general, be benchmark with the weight of negative electrode active material, the consumption of described solvent is 100-150 weight %.Wherein, drying, the method for calendering and condition are conventionally known to one of skill in the art.
Lithium ion battery provided by the present invention comprises pole piece and nonaqueous electrolytic solution, and described pole piece and nonaqueous electrolytic solution are sealed in the battery container, and described pole piece comprises positive pole, negative pole and barrier film.Except using, can use conventional positive pole, barrier film, nonaqueous electrolytic solution by the negative pole provided by the invention.
Described barrier film is arranged between positive pole and the negative pole, and it has electrical insulation capability and liquid retainability energy, and described pole piece and nonaqueous electrolytic solution are contained in the battery case together.Described barrier film can be selected from various barrier films used in the lithium ion battery, as being nonwoven fabrics, synthetic resin microporous barrier, as microporous polyolefin film, microporous polypropylene membrane, polyethylene polypropylene composite micro porous film.The position of described barrier film, character and kind are conventionally known to one of skill in the art.
Consisting of of described positive pole is conventionally known to one of skill in the art.In general, positive pole comprises collector body and coating and/or is filled in positive electrode on the collector body that described positive electrode comprises positive active material, conductive agent and anodal adhesive.
Described positive active material is not particularly limited, and can be the positive active material of the embedded removal lithium embedded of this area routine, a kind of or its mixture: the Li in the preferred following material
xNi
1-yCoO
2(wherein, 0.9≤x≤1.1,0≤y≤1.0), Li
1+aM
bMn
2-bO
4(wherein ,-0.1≤a≤0.2,0≤b≤1.0, M is a kind of in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur), Li
mMn
2-nB
nO
2(wherein, B is a transition metal, 0.9≤m≤1.1,0≤n≤1.0).
Described conductive agent is not particularly limited, and can be the anodal conductive agent of this area routine, at least a such as in acetylene black, conductive carbon black and the electrically conductive graphite.Weight with positive active material is benchmark, and the content of described conductive agent is 1-15 weight %, is preferably 2-10 weight %.
The kind of described anodal adhesive and content are conventionally known to one of skill in the art, for example one or more in fluorine resin and polyolefin compound such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) and butadiene-styrene rubber (SBR) and the polyvinyl alcohol.In general, according to the difference of used anodal adhesive kind, be benchmark with the weight of positive active material, the content of anodal adhesive is 0.5-15 weight %, is preferably 1-15 weight %.
Positive electrode collector can be positive electrode collector conventional in the lithium ion battery, uses aluminium foil as positive electrode collector in specific embodiments of the present invention.
The preparation method of described positive pole can adopt conventional preparation method.For example, with described positive active material, conductive agent and adhesive and solvent, apply and/or be filled on the described collector body, drying is rolled or is not rolled, and can obtain described positive pole.
Under the preferable case, the preparation method of described positive pole comprises that the slurry that will contain positive active material, conductive agent and anodal adhesive and solvent applies and/or is filled on the collector body, dry, roll or do not roll, wherein, described solvent can be selected from one or more in N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols.The consumption of solvent can make described pastel have viscosity and flowability, can be coated on the described collector body to get final product.In general the weight with positive active material is benchmark, and the content 30-80 weight % of described solvent is preferably 35-60 weight %.Wherein, drying, the method for calendering and condition are conventionally known to one of skill in the art.
Described nonaqueous electrolytic solution is the mixed solution of electrolyte lithium salt and nonaqueous solvents, and it is not particularly limited, and can use the nonaqueous electrolytic solution of this area routine.Be selected from lithium hexafluoro phosphate (LiPF such as electrolyte lithium salt
6), in lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and the fluorocarbon based sulfonic acid lithium one or more.Organic solvent is selected chain acid esters and ring-type acid esters mixed solution for use, wherein the chain acid esters can be dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other are fluorine-containing, sulfur-bearing or contain at least a in the chain organosilane ester of unsaturated bond, the ring-type acid esters can be ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton (γ-BL), sultone and other are fluorine-containing, sulfur-bearing or contain at least a in the ring-type organosilane ester of unsaturated bond.The injection rate of electrolyte is generally 1.5-4.9g/Ah, the concentration of electrolyte be generally 0.5-2.9 rub/liter.In addition, can also in electrolyte, add and can promote the film formed additive of SEI, as PS, VC etc.
According to the preparation method of lithium ion battery provided by the invention, except described negative pole prepared according to method provided by the invention, other step was conventionally known to one of skill in the art.In general,, pole piece and the electrolyte that obtains is sealed in the battery case, can obtains lithium ion battery provided by the invention the described positive pole for preparing and negative pole and pole piece of barrier film formation.
To specifically describe the present invention by embodiment below.
Embodiment 1
Present embodiment illustrates preparation and the negative pole and the battery of negative electrode active material provided by the invention.
(1) preparation of negative electrode active material
With Al (NO
3)
3Mix with absolute ethyl alcohol (alcohol), obtaining concentration is the Al (NO of 1.86 weight %
3)
3Solution, and with material with carbon element graphite and above-mentioned Al (NO
3)
3Solution mixes, described graphite and Al (NO
3)
3Al (NO in the solution
3)
3Weight ratio be 100:1.25, after 80 ℃ of oven dry, put into 400 ℃ of high temperature furnace sintering 4 hours, obtain the graphite that the surface is coated with aluminium oxide.Total amount with negative electrode active material is a benchmark, and the content of material with carbon element graphite is 99.70 weight %, and the content of aluminium oxide is 0.30 weight %.
(2) preparation of negative pole
Negative electrode active material, 1 weight portion microparticle graphite (particle diameter is the 0.5-6 micron), 2 weight portion bonding agent PTFE that 100 weight portion steps (1) are obtained join in 100 weight parts waters, stir then to form uniform cathode size.
This slurry is coated on the Copper Foil equably, then in 90 ℃ of following oven dry, roll-in, cut to make and be of a size of 394 * 41 millimeters negative pole, wherein contain the graphite that 2.6 gram negative electrode active materials are coated with aluminium oxide.
(2) Zheng Ji preparation
With the anodal active component LiCoO of 100 weight portions
2, 15 weight portion polyvinylidene fluoride PVDF, 4 weight portion conductive agent acetylene blacks join among the 50 weight portion N-N-methyl-2-2-pyrrolidone N-NMP, stir then and form uniform anode sizing agent.
This slurry is coated on the aluminium foil equably, 150 ℃ of following oven dry, roll-ins then, cuts to make and be of a size of 390 * 40 millimeters positive pole, wherein contain 5.8 gram active component LiCoO
2
(3) assembling of battery
Above-mentioned positive and negative electrode and 18 microns * 44 millimeters (PP/PE/PP) Celgard diaphragm papers are wound into the pole piece of a square lithium ion battery, subsequently with LiPF
6Be dissolved in by the concentration of 1 mol in the mixed solvent of EC/DMC=1:1 and form nonaqueous electrolytic solution, this electrolyte injected 4.0 * 34 * 46 millimeters rectangular cell shell with the amount of 2.4g/Ah, sealing, making design capacity is 800 MAHs, model is LP463446ARU lithium ion battery A1.
Embodiment 2
Present embodiment illustrates preparation and the negative pole and the battery of negative electrode active material provided by the invention.
Method according to embodiment 1 prepares negative electrode active material, negative pole and lithium ion battery, and different is, in the preparation process of negative electrode active material, and described material with carbon element graphite and Al (NO
3)
3Weight ratio be 100:0.8, in the negative electrode active material that obtains, be benchmark with the total amount of negative electrode active material, the content of material with carbon element graphite is 99.80 weight %, the content of aluminium oxide is 0.20 weight %.Prepare lithium ion battery A2.
Embodiment 3
Present embodiment illustrates preparation and the negative pole and the battery of negative electrode active material provided by the invention.
Method according to embodiment 1 prepares negative electrode active material, negative pole and lithium ion battery, and different is, in the preparation process of negative electrode active material, and described material with carbon element graphite and Al (NO
3)
3Weight ratio be 100:7.0, in the negative electrode active material that obtains, be benchmark with the total amount of negative electrode active material, the content of material with carbon element graphite is 98.40 weight %, the content of aluminium oxide is 1.60 weight %.Prepare lithium ion battery A3.
Embodiment 4
Present embodiment illustrates preparation and the negative pole and the battery of negative electrode active material provided by the invention.
Method according to embodiment 1 prepares negative electrode active material, negative pole and lithium ion battery, and different is that in the preparation process of negative pole, the addition of described conductive agent microparticle graphite is 0.2 weight portion, prepares lithium ion battery A4.
Embodiment 5
Present embodiment illustrates preparation and the negative pole and the battery of negative electrode active material provided by the invention.
Method according to embodiment 1 prepares negative electrode active material, negative pole and lithium ion battery, and different is that in the preparation process of negative pole, the addition of described conductive agent microparticle graphite is 3 weight portions, prepares lithium ion battery A5.
Embodiment 6
Present embodiment illustrates preparation and the negative pole and the battery of negative electrode active material provided by the invention.
Method according to embodiment 1 prepares negative electrode active material, negative pole and lithium ion battery, and different is, in the preparation process of negative pole, does not add conductive agent microparticle graphite, prepares lithium ion battery A6.
Embodiment 7
Present embodiment illustrates preparation and the negative pole and the battery of negative electrode active material provided by the invention.
Method according to embodiment 1 prepares negative electrode active material, negative pole and lithium ion battery, and different is that the temperature of sintering is 500 ℃, prepares lithium ion battery A7.
Embodiment 8
Present embodiment illustrates preparation and the negative pole and the battery of negative electrode active material provided by the invention.
Method according to embodiment 1 prepares negative electrode active material, negative pole and lithium ion battery, and different is, in the preparation process of negative electrode active material, with Ba (NO
3)
2Mix with deionized water, obtaining concentration is the Ba (NO of 1.48 weight %
3)
2Solution, and with material with carbon element graphite and above-mentioned Ba (NO
3)
2Solution mixes, described graphite and Ba (NO
3)
2Ba (NO in the solution
3)
2Weight ratio be 100:1.25, after 80 ℃ of oven dry, under protection of nitrogen gas, put into 600 ℃ of high temperature furnace sintering 4 hours, obtain the surface and be coated with barytic graphite.Total amount with negative electrode active material is a benchmark, and the content of material with carbon element graphite is 99.27 weight %, and barytic content is 0.73 weight %.And prepare battery cathode and battery according to the method for embodiment 1, obtain lithium rechargeable battery A8.
Embodiment 9
Present embodiment illustrates preparation and the negative pole and the battery of negative electrode active material provided by the invention.
Method according to embodiment 1 prepares negative electrode active material, negative pole and lithium ion battery, and different is, in the preparation process of negative electrode active material, with Zn (NO
3)
2Mix with deionized water, obtaining concentration is the Zn (NO of 5.92 weight %
3)
2Solution, and with material with carbon element graphite and above-mentioned Zn (NO
3)
2Solution mixes, described graphite and Zn (NO
3)
2Zn (NO in the solution
3)
2Weight ratio be 100:5.0, after 80 ℃ of oven dry, put into 400 ℃ of high temperature furnace sintering 4 hours, obtain the graphite that the surface is coated with zinc oxide.Total amount with negative electrode active material is a benchmark, and the content of material with carbon element graphite is 97.90 weight %, and the content of zinc oxide is 2.10 weight %.And prepare battery cathode and battery according to the method for embodiment 1, obtain lithium rechargeable battery A9.
Embodiment 10
Present embodiment illustrates preparation and the negative pole and the battery of negative electrode active material provided by the invention.
Method according to embodiment 1 prepares negative electrode active material, negative pole and lithium ion battery, and different is, in the preparation process of negative electrode active material, with Ti (NO
3)
4Mix with deionized water, obtaining concentration is the Ti (NO of 0.474 weight %
3)
4Solution, and with material with carbon element graphite and above-mentioned Ti (NO
3)
4Solution mixes, described graphite and Ti (NO
3)
4Ti (NO in the solution
3)
4Weight ratio be 100:0.68, after 80 ℃ of oven dry, put into 400 ℃ of high temperature furnace sintering 4 hours, obtain the graphite that the surface is coated with titanium oxide.Total amount with negative electrode active material is a benchmark, and the content of material with carbon element graphite is 99.81 weight %, and the content of titanium oxide is 0.19 weight %.And prepare battery cathode and battery according to the method for embodiment 1, obtain lithium rechargeable battery A10.
Comparative Examples 1
The preparation of this Comparative Examples explanation reference cell.
Method according to embodiment 1 prepares battery, and different is that when the preparation battery cathode, used negative electrode active material is the not graphite of coated metal oxide of surface, prepares reference lithium ion battery AC1.
Comparative Examples 2
The preparation of this Comparative Examples explanation reference cell.
Method according to the disclosed embodiment 1 of CN1679185A prepares barrier film, and prepares battery according to the method for embodiment 6, obtains reference lithium ion battery AC2.
Embodiment 11-20
The following example is measured the cycle performance of the lithium ion battery A1-A10 that embodiment 1-10 makes and the test of security performance respectively.
1, cycle performance test: at ambient temperature, with battery respectively with 1C (750 MAH) current charges to 4.2V, with constant-potential charge, cut-off current is 0.05C after voltage rises to 4.2V, shelves 10 minutes; Battery, was shelved 5 minutes to 3.0V with 1C (750 MAH) current discharge.Repeat above step 400 time, obtain the capacity after 400 circulations of battery, by capacity sustainment rate before and after the following formula computation cycles:
Capacity sustainment rate=(the 400th cyclic discharge capacity/cyclic discharge capacity) first * 100%
The result is as shown in table 1.
2, security performance test:
1) overcharges test: under 25 ℃, electric current with 0.5C (375 MAH) lies prostrate battery constant voltage charge to 4.2, cut-off current is 8 milliamperes, then, with electric current constant voltage charge to 5 volt of this battery with 1A, continue charging 2 hours, whether the observation battery blasts, the on fire or phenomenon of leakage, and the maximum temperature of test battery.
2) lancing test: under 25 ℃, with battery constant voltage charge to 4.2 volt, cut-off current is 8 milliamperes with the electric current of 0.5C (375 MAH).Battery is fixed with anchor clamps, battery is stung fully, observe whether battery blasts, the on fire or phenomenon of leakage with the rustless steel nail of 3.12 mm wides, 76.2 millimeters long, and the maximum temperature of test battery.
3) furnace temperature test: under 25 ℃, with battery constant voltage charge to 4.2 volt, cut-off current is 8 milliamperes with the electric current of 0.5C (375 MAH).Battery is put into baking box, be warming up to 150 ℃ with 5 ℃/minute programming rates, constant temperature is placed, and whether the observation battery blasts, the on fire or phenomenon of leakage, and the maximum temperature of test battery.The result is as shown in table 2.
3, internal resistance of cell test:
Battery is placed on respectively on the BS-VR3 Intelligentized battery internal resistance test device (Qingtian Industry Co., Ltd., Guangzhou), measurand is applied the 1KHz AC signal, obtain its internal resistance by measuring its interchange pressure drop.The result is as shown in table 1.
Comparative Examples 3-4
The reference lithium ion battery AC1 that this Comparative Examples mensuration Comparative Examples 1 and Comparative Examples 2 make, cycle performance and the security performance of AC2.
Adopt with embodiment 11-18 in identical method measure, different is that the battery of mensuration is reference lithium ion battery AC1 and AC2.
The result is as shown in table 1.
Table 1
| The embodiment numbering | The battery numbering | Capacity sustainment rate (%) | The internal resistance of cell (milliohm) |
| Embodiment 11 | A1 | 86.3 | 48.2 |
| Comparative Examples 3 | AC1 | 80.2 | 47.3 |
| Embodiment 12 | A2 | 84.9 | 47.6 |
| Embodiment 13 | A3 | 88.5 | 48.8 |
| Embodiment 14 | A4 | 83.3 | 49.0 |
| Embodiment 15 | A5 | 87.1 | 47.4 |
| Embodiment 16 | A6 | 82.8 | 49.6 |
| Embodiment 17 | A7 | 86.5 | 48.3 |
| Embodiment 18 | A8 | 86.0 | 48.1 |
| Embodiment 19 | A9 | 88.6 | 48.6 |
| Embodiment 20 | A10 | 83.5 | 47.5 |
| Comparative Examples 4 | AC2 | 82.5 | 48.3 |
Table 2
In the test result from last table 2 as can be seen, lithium ion battery by negative electrode active material preparation of the present invention, when overcharging performance test, the maximum temperature of battery of the present invention all is lower than 61 ℃, the maximum temperature of reference cell is respectively 497 ℃ and 75 ℃, and reference cell has the phenomenon on fire of generation; When carrying out lancing test, the maximum temperature of battery of the present invention all is lower than 54 ℃, and the maximum temperature of reference cell is respectively 205 ℃ and 62 ℃, and reference cell has the phenomenon on fire of generation; When carrying out the furnace temperature test, the maximum temperature of battery of the present invention all is lower than 153 ℃, the maximum temperature of reference cell is respectively 350 ℃ and 158 ℃, and reference cell has the battery explosion of generation, phenomenon on fire, by The above results as can be known, the battery that is prepared by negative electrode active material of the present invention has good security performance, in addition, result in the last table 1 as can be seen, after charge and discharge cycle 400 times, the capacity sustainment rate of battery illustrates that all more than 82.8% battery of the present invention has good electrochemical simultaneously.
Claims (11)
1, a kind of lithium ion battery negative pole active materials, it is characterized in that, this negative electrode active material contains material with carbon element and metal oxide, described metal oxide is coated on the surface of material with carbon element, and described metal oxide is selected from one or more in the oxide of IIA in the periodic table of elements, IIIA, IB, IIB, IIIB and IVB family metal.
2, negative electrode active material according to claim 1, wherein, described metal oxide is selected from MgO, Al
2O
3, CuO, ZnO, TiO
2, BaO and ZrO
2In one or more.
3, negative electrode active material according to claim 1 wherein, is a benchmark with the total amount of negative electrode active material, and the content of described material with carbon element is 97.0-99.9 weight %, and the content of described metal oxide is 0.1-3.0 weight %.
4, negative electrode active material according to claim 3 wherein, is a benchmark with the total amount of negative electrode active material, and the content of described material with carbon element is 98.0-99.8 weight %, and the content of described metal oxide is 0.2-2.0 weight %.
5, negative electrode active material according to claim 1, wherein, described material with carbon element is selected from one or more in native graphite, Delanium, petroleum coke, organic cracking carbon, pyrolysis resin carbon, carbonaceous mesophase spherules and the carbon fiber.
6, the preparation method of the described lithium ion battery negative pole active materials of claim 1, it is characterized in that, this method comprises material with carbon element, soluble metallic salt and solvent, dry then, and at 400-500 ℃ of following sintering, described soluble metallic salt is selected from one or more in the soluble metallic salt of IIA in the periodic table of elements, IIIA, IB, IIB, IIIB and IVB family metal.
7, method according to claim 6, wherein, described soluble metallic salt is selected from Mg (NO
3)
2, Al (NO
3)
3, Cu (NO
3)
2, Zn (NO
3)
2, Ti (NO
3)
4, Ba (NO
3)
2And Zr (NO
3)
4In one or more.
8, method according to claim 6, wherein, the consumption of described material with carbon element and soluble metallic salt makes in the negative electrode active material that obtains, and the content of metal oxide and material with carbon element is respectively the 0.1-3.0 weight % and the 97.0-99.9 weight % of negative electrode active material total amount.
9, a kind of negative pole of lithium ion battery, this negative pole comprises collector body and the negative material that loads on this collector body, described negative material contains negative electrode active material and adhesive, it is characterized in that, described negative electrode active material is any described negative electrode active material among the claim 1-5.
10, negative pole according to claim 9, wherein, also contain conductive agent in the described negative material, described conductive agent is selected from one or more in microparticle electrographite, acetylene black, conductive carbon black, electrically conductive graphite and the carbon fiber, weight with described negative electrode active material is benchmark, and the content of described conductive agent is 0.2-3.0 weight %.
11, a kind of lithium ion battery, this battery comprises pole piece and nonaqueous electrolytic solution, and described pole piece and nonaqueous electrolytic solution are sealed in the battery container, and described pole piece comprises positive pole, negative pole and barrier film, it is characterized in that, and described negative pole is the described negative pole of claim 9.
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