CN101192662A - Battery cathode and lithium ion secondary battery comprising same - Google Patents

Battery cathode and lithium ion secondary battery comprising same Download PDF

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CN101192662A
CN101192662A CNA2006101611135A CN200610161113A CN101192662A CN 101192662 A CN101192662 A CN 101192662A CN A2006101611135 A CNA2006101611135 A CN A2006101611135A CN 200610161113 A CN200610161113 A CN 200610161113A CN 101192662 A CN101192662 A CN 101192662A
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electrographite
native graphite
flakey
microparticle
graphite
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CN100557860C (en
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刘卫平
李科
姜俊刚
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BYD Co Ltd
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BYD Co Ltd
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    • YGENERAL 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
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    • Y02E60/10Energy storage using batteries

Abstract

The invention relates to a cathode of a lithium ion secondary battery, comprising a current collector and cathode material smeared over and/or filled in the current collector. The cathode material comprises cathode active substance and cathode adhesive. The cathode active substance is the mixture of a natural graphite and an artificial graphite, wherein, the natural graphite is the natural graphite with a ball shape, the artificial graphite is the artificial graphite with a micro granule scaly shape, the particle diameter of the natural graphite with the ball shape is longer than that of the artificial graphite with the micro granule scaly shape, the difference in value of the median diameter D50 between the natural graphite with the ball shape and the artificial graphite with the micro granule scaly shape is 4-25 microns; the median diameter D50 of the artificial graphite with the micro granule scaly shape is 0. 3-6 microns; the proportion by weight between the natural graphite with the ball shape and the artificial graphite with the micro granule scaly shape is 1:0.05-0.2. The lithium ion secondary battery provided by the invention has good circle performance and discharging performance with a large rate and safety performance under the condition of high capacity.

Description

Battery cathode and comprise the lithium rechargeable battery of this negative pole
Technical field
The invention relates to a kind of battery cathode and comprise the battery of this negative pole, specifically, the invention relates to a kind of battery cathode and comprise the lithium rechargeable battery of this negative pole.
Background technology
Lithium rechargeable battery is as a kind of novel chemical power source, have high-energy-density, high voltage, pollution-free, characteristics such as containing metal lithium, cycle life height, memory-less effect, charging rate be not fast, being widely used in 3C Product, also is in PC, mobile phone and the individual radio electronic equipment such as portable CD player, PDA.
Yet along with improving constantly of people's demand, the high-capacity lithium-ion secondary cell has become the trend of present development.For making lithium rechargeable battery have higher capacity and outstanding combination property, the most basic approach is to improve the performance of positive active material and negative electrode active material.At present, negative electrode active material makes graphite with the most use, and people make improvements with different modes continuous the trial.
Graphite comprises electrographite and native graphite, and the two respectively has pluses and minuses.For electrographite, it has good cycle, the advantage that stereomutation is little, but its shortcoming is that electrographite often is difficult to the degree of graphitization that reaches high, and specific capacity is little, be exactly often to be difficult to compacting in addition at the electrographite that carries out with easy graphitized carbon obtaining after the graphitization processing, the volume energy density of the negative plate that calendering obtains is low, cause battery capacity low, and negative material also is easy to come off from collector electrode.For native graphite, it has the specific capacity height, is easy to advantages such as compacting, but the expansion and the collapse of graphite linings easily take place in charge and discharge process for it, cause cycle performance relatively poor, and heavy-current discharge performance neither be very desirable.
For adapting to the requirement of lithium rechargeable battery development, people mainly improve the performance of graphite from the following aspects:
(1) for electrographite, the method that the researcher usually adopts is that at high temperature (generally more than 2500 ℃) reach hundreds of hours insulation with graphite, and making the electrographite of high graphitization degree, but this method efficient is low, energy consumption is big, cost is high;
(2) for native graphite, the method that the researcher adopts usually is that the native graphite surface is coated processing, obtains the composite graphite of " shell-nuclear " structure, to suppress the structural change of native graphite in cyclic process.Yet in fact, this effect is very limited, and the cycle performance of native graphite still is difficult to satisfy people's requirement in actual applications, and this coating layer often do not possess embedding lithium function, also can reduce the specific capacity that coats the back native graphite;
(3) because electrographite and native graphite respectively have pluses and minuses, therefore, many researchers often adopt the negative electrode active material of the admixed graphite of electrographite and native graphite as lithium rechargeable battery, to bring into play the advantage of two kinds of graphite, remedy shortcoming each other.
CN1702892A discloses a kind of composite graphite negative electrode material of lithium rechargeable battery, it is characterized in that, described graphite comprises modified natural graphite and Delanium, and the mass ratio of described native graphite and Delanium is 30: 70-80: 20.Wherein, the average grain diameter of described modified natural graphite is the 5-35 micron, and the average grain diameter of described Delanium is the 2-20 micron.
Though this negative material adopts the admixed graphite of native graphite and electrographite as negative electrode active material, but, find in actual applications, the ratio of native graphite often can not be too high in the admixed graphite of prior art, generally be lower than 80% of admixed graphite total weight, the content of described native graphite can not too high reason be, the too high levels of native graphite can worsen the cycle performance of battery, thereby, adopt to add the cycle performance that Delanium improves battery, but adopt the battery specific capacity of the admixed graphite of such ratio but to be difficult to reach the requirement of high-capacity lithium-ion secondary cell.
CN1808745A discloses a kind of negative pole of lithium rechargeable battery, the negative electrode active material that this negative pole adopted comprises the admixed graphite of being made up of flakey native graphite, spherical natural graphite and flakey Delanium, wherein, the flakey native graphite accounts for the 35-70 weight % of admixed graphite total weight, spherical native graphite accounts for the 5-45 weight % of admixed graphite total weight, and the flakey Delanium accounts for the 5-30 weight % of admixed graphite total weight.
The negative pole of this lithium rechargeable battery adopts the admixed graphite of three kinds of graphite as negative electrode active material, cycle performance obtains improvement to a certain extent, but, in this negative electrode active material, compare with the amount of Delanium, though two kinds of amounts of mixing native graphite are higher, but, because the flakey native graphite is not easy compacting, its volume energy density is lower than spherical native graphite, and therefore the volume density of the negative plate that obtains after the admixed graphite of spherical native graphite, flakey native graphite and Delanium is rolled only is the 1.55-1.60 gram-centimeter 3, this explanation, the amount of the negative electrode active material on unit volume is limited, thereby causes the specific capacity of battery lower, all is no more than 340 MAH/grams basically, and this is less-than-ideal for making the lithium rechargeable battery of high power capacity.
In sum, the admixed graphite that adopts prior art all is difficult to take into account as the battery of negative electrode active material and makes battery have high power capacity and good circulation performance demands.
Summary of the invention
The negative pole that the objective of the invention is to overcome existing lithium rechargeable battery can not be taken into account the shortcoming that battery has high power capacity and good cycle performance of battery, and a kind of negative pole that makes lithium rechargeable battery have the high and good circulation performance of capacity is provided.
Second purpose of the present invention provides the preparation method of above-mentioned negative pole.
The 3rd purpose of the present invention provides the lithium rechargeable battery that uses above-mentioned negative pole.
The present inventor finds, we recognize by prior art, in the admixed graphite that adopts native graphite and electrographite during as negative electrode active material, though the content that improves native graphite can improve the specific capacity of battery, but prior art is instructed us, even added electrographite, if still can cause the deterioration of cycle performance of battery for the capacity of taking battery into account makes the too high levels of native graphite.In addition, in the admixed graphite that adopts spherical native graphite and flakey native graphite and flakey Delanium during as negative electrode active material, though two kinds of native graphites, promptly, the total amount of spherical native graphite and flakey native graphite is than high many of the content of native graphite in the existing admixed graphite, but, because the flakey native graphite is not easy compacting, its volume energy density is lower than spherical native graphite, therefore with spherical native graphite, the volume density of the negative plate that obtains after the admixed graphite of flakey native graphite and Delanium is rolled is also lower, even the ratio that the mixing total amount of such two kinds of native graphites accounts for is higher, but but can not effectively improve battery capacity and the cycle performance that improves battery simultaneously.And through research, the present inventor finds, the microparticle flakey electrographite of small particle diameters will mix with spherical native graphite by having more, utilize the complementation of the particle diameter of described two class graphite, not only can improve the arrangement mode of graphite, thereby microparticle flakey electrographite is filled in the slit of spherical native graphite, improved the cycle performance of battery, simultaneously can also effectively guarantee the content of spherical native graphite in admixed graphite, guarantee that battery has high power capacity, reach the purpose of improving battery capacity and cycle performance simultaneously then.
The invention provides a kind of negative pole of lithium rechargeable battery, this negative pole comprises collector body and coating and/or is filled in negative material on this collector body, described negative material comprises negative electrode active material and negative pole adhesive, described negative electrode active material is the mixture of native graphite and electrographite, wherein, described native graphite is spherical native graphite, described electrographite is a microparticle flakey electrographite, the particle diameter of described spherical native graphite is greater than the particle diameter of microparticle flakey electrographite, the median particle diameter D of described spherical native graphite and microparticle flakey electrographite 50Difference is the 4-25 micron; The median particle diameter D of described microparticle flakey electrographite 50Be the 0.3-6 micron; The weight ratio of described spherical native graphite and microparticle flakey electrographite is 1: 0.05-0.2.
The invention provides the preparation method of above-mentioned battery cathode, this method comprises that the slurry that will contain negative material applies and/or is filled on the collector body, dry, calendering, described negative material comprises negative electrode active material and negative pole adhesive, described negative electrode active material is the mixture of native graphite and electrographite, wherein, described native graphite is spherical native graphite, described electrographite is a microparticle flakey electrographite, the particle diameter of described spherical native graphite is greater than the particle diameter of microparticle flakey electrographite, the median particle diameter D of described spherical native graphite and microparticle flakey electrographite 50Difference is the 4-25 micron; The median particle diameter D of described microparticle flakey electrographite 50Be the 0.3-6 micron; The weight ratio of described spherical native graphite and microparticle flakey electrographite is 1: 0.05-0.2.
The present invention also provides a kind of lithium rechargeable battery, and this battery comprises battery container and is sealed in this battery container interior electrode group and electrolyte; Described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and wherein, described negative pole is a negative pole provided by the invention.
Because negative electrode active material of the present invention is the admixed graphite of spherical native graphite and flakey Delanium, and the weight ratio of described spherical native graphite and microparticle flakey electrographite is 1: 0.05-0.2, such mixed proportion is to be key component with spherical native graphite, be aided with the higher microparticle flakey electrographite of a small amount of degree of graphitization simultaneously, thereby guaranteed that this negative material has high volume energy density, the specific capacity height.Though only added a small amount of microparticle flakey electrographite, can too much not influence the cycle performance of battery because of the content of spherical native graphite, because, described median particle diameter D 50For the numbers of particles of the microparticle flakey electrographite of 0.3-6 micron is several times as much as native graphite, these microparticle flakey electrographites are full of around spherical native graphite, after in the compressing tablet process, applying certain pressure, spherical native graphite and microparticle flakey electrographite have on every side formed the composite graphite of a kind of actual " shell-nuclear " structure, effectively suppressed the structural change of spherical native graphite in the cyclic process, thereby guarantee that only needing to add a spot of this electrographite just can significantly improve the cycle performance and the heavy-current discharge performance of native graphite, has taken into account high power capacity thereby satisfied described lithium ion battery, excellent comprehensive performances such as good circulation performance and heavy-current discharge performance.In addition, the preparation method who the invention provides battery cathode is very simple, is easy to industrialization, and is used for the negative material of high-capacity lithium-ion secondary cell with respect to other, and is with low cost.
Description of drawings
Fig. 1 is that spherical native graphite amplifies 1000 times electromicroscopic photograph;
Fig. 2 is that microparticle flakey electrographite amplifies 1000 times electromicroscopic photograph;
Fig. 3 is that the admixed graphite of spherical native graphite and microparticle flakey electrographite is amplified 1000 times electromicroscopic photograph;
Fig. 4 is the distribution schematic diagram of the spherical native graphite before mixing with microparticle flakey electrographite;
As 5 is with spherical native graphite and the mixed distribution schematic diagram of microparticle flakey electrographite.
Description of reference numerals
1---native graphite 2---electrographite
Embodiment
Battery cathode provided by the invention comprises collector body and coating and/or is filled in negative material on this collector body, described negative material comprises negative electrode active material and negative pole adhesive, described negative electrode active material is the mixture of native graphite and electrographite, wherein, described native graphite is spherical native graphite, described electrographite is a microparticle flakey electrographite, the particle diameter of described spherical native graphite is greater than the particle diameter of microparticle flakey electrographite, the median particle diameter D of described spherical native graphite and microparticle flakey electrographite 50Difference is the 4-25 micron; The median particle diameter D of described microparticle flakey electrographite 50Be the 0.3-6 micron; The weight ratio of described spherical native graphite and microparticle flakey electrographite is 1: 0.05-0.2.
Negative electrode active material of the present invention is the admixed graphite of native graphite and electrographite, and wherein, described native graphite is spherical native graphite, and described electrographite is a microparticle flakey electrographite.This negative electrode active material is to be the key component of negative electrode active material with spherical native graphite, on this basis, adds a spot of microparticle flakey electrographite.The weight ratio of described spherical native graphite and microparticle flakey electrographite is 1: 0.05-0.2 is preferably 1: 0.05-0.15.Above-mentioned mixed proportion makes spherical native graphite account for more than 83% of negative electrode active material total weight at least, therefore, make the initial discharge capacity of spherical native graphite in electrolyte can reach 370 MAHs/more than the gram, thereby lay a good foundation for this admixed graphite has high specific capacity.
According to the present invention, described native graphite is spherical native graphite, and this spherical native graphite can be commercially available also and can prepare according to the method for well known to a person skilled in the art.The pattern of described spherical native graphite is shown in the electromicroscopic photograph of Fig. 1.
The median particle diameter D of described spherical native graphite 50Be the 10-30 micron, be preferably the 12-25 micron; Microcrystalline coating interplanar distance d 002Be the 0.3354-0.3380 nanometer, the specific area that adopts cryogenic nitrogen absorption BET method to obtain is a 0.5-3 rice 2/ gram.
According to the present invention, described electrographite is a microparticle flakey electrographite, this microparticle flakey electrographite can be commercially available also can be prepared as follows and obtain: as, easy graphitized charcoal (as the pitch coke etc.) is carried out high temperature graphitization under 1900-2800 ℃ in nitrogen atmosphere handle, temperature retention time under the high temperature is decided by the height that degree of graphitization requires, degree of graphitization requires high more, and temperature retention time is long more.Generally speaking, the time of soak can be 24-480 hour.And then cooled graphite carried out the intensity air classification and make.The pattern of described microparticle flakey electrographite is shown in the electromicroscopic photograph of Fig. 2.
The median particle diameter D of described microparticle flakey electrographite 50Be the 0.3-6 micron, be preferably the 0.5-1.8 micron.If the undersized of described microparticle flakey electrographite, then this electrographite is easy to reunite, and is not easy to be uniformly dispersed in spherical native graphite, does not reach the effect of improving the native graphite cycle performance on the contrary; If its grain graininess is excessive, then under the certain situation of this electrographite addition, this electrographite numbers of particles that distributes around the native graphite reduces, and makes that the contact point between native graphite and the adjacent graphite reduces, and makes the monolithic conductive decreased performance of negative electrode active material; In addition, if the granularity of described microparticle flakey electrographite is excessive, under the little situation of this electrographite surface topography difference, specific area can reduce, thereby influence the permeance property of electrolyte, also be not easy to the gap between the filled natural graphite, thereby one can cause the volume energy density of cathode pole piece to can not get improving, the two then can not effectively suppress the change of native graphite structure.Therefore, the median particle diameter D of described microparticle flakey electrographite 50Be preferably the 0.3-6 micron, more preferably the 0.5-1.8 micron.
Though the specific capacity of described microparticle flakey electrographite is low with respect to spherical native graphite, but under the less situation of this electrographite addition, to guarantee can not reduce the specific capacity of whole admixed graphite on the one hand, guarantee again that on the other hand this electrographite has higher degree of graphitization, therefore, the microcrystalline coating interplanar distance d of described microparticle flakey electrographite 002Be the 0.3354-0.3400 nanometer, the specific area that adopts cryogenic nitrogen absorption BET method to obtain is a 10-25 rice 2/ gram.
According to the present invention, the weight ratio of described spherical native graphite and microparticle flakey electrographite is 1: 0.05-0.2.Though the amount of electrographite is less with respect to native graphite, only be the 5-20% of native graphite weight, but because described electrographite is a microparticle flakey electrographite, its particle is very tiny with respect to spherical native graphite, thereby make spherical native graphite around distributing this microparticle flakey electrographite a large amount of, this has improved the electric conductivity of negative pole greatly.
Suppose with particle diameter to be that the microparticle flakey electrographite that 16 microns spherical native graphite and particle diameter are 2 microns mixes with 10: 1 weight ratio, the ratio of the granule number of the granule number of spherical native graphite and microparticle flakey electrographite can calculate by following formula in this admixed graphite so:
Figure A20061016111300101
Figure A20061016111300111
By above calculating as can be known, be after 2 microns microparticle flakey electrographite mixes with 10: 1 mass ratio, around each spherical natural graphite particles, to be evenly distributed 51.2 microparticle flakey electrographite particles with particle diameter when the spherical native graphite and the particle diameter that are 16 microns.
As shown in Figure 4, not with spherical native graphite with when this microparticle electrographite mixes, the contact point between the two adjacent natural graphite particles is comparatively single; In addition, as shown in Figure 5, added in described spherical native graphite after a small amount of microparticle flakey electrographite, this electrographite that is several times as much as the natural graphite particles number is full of between adjacent native graphite, makes that the contact area between the adjacent native graphite is widened greatly.And, under the certain pressure calendering, can make the arrangement of described spherical native graphite and microparticle flakey electrographite become more tight, help the improvement of negative pole electric conductivity.In addition, this arrangement closely makes described native graphite and this microparticle electrographite on every side form a kind of actual " shell-nuclear " structure composite graphite, can effectively suppress the defective that the native graphite structure easily expands, collapses and changes in the battery cyclic process, improve and improved the cycle performance and the heavy-current discharge performance of battery then.
In addition, this microparticle electrographite provided by the invention has bigger specific area, is very beneficial for the absorption and the infiltration of electrolyte.When described microparticle electrographite is scattered between the spherical native graphite uniformly, because the microparticle electrographite absorbability very strong to electrolyte, thereby driven the abundant infiltration of electrolyte between whole admixed graphite.This is very favorable to form uniform and stable SEI film at graphite surface, and also favourable and lithium ion freely embeds in graphite and deviates from, and has reduced because of local insufficient electrolyte causes the SEI film and has been decreased and produce the risk of Li dendrite.
Therefore, in sum, for the cycle performance that effectively improves battery, heavy-current discharge performance with and guarantee that battery has higher capacity, the suitable weight ratio of described spherical native graphite and microparticle flakey electrographite is preferably 1: 0.05-0.2, more preferably 1: 0.05-1.5.
According to the present invention, described method with spherical native graphite and the mixing of microparticle flakey electrographite can adopt the known conventional method of art technology, mixes as mechanical mixture or ball milling.For example, when carrying out mechanical mixture, can directly two kinds of graphite be added simultaneously in the mixer mechanical mixture 100-300 minute; When carrying out the ball milling mixing, can directly two kinds of graphite be put into ball mill ball milling mixing 30-100 minute simultaneously, can obtain the admixed graphite of described spherical native graphite and microparticle flakey electrographite.The electromicroscopic photograph of the described admixed graphite that obtains after spherical native graphite and microparticle flakey electrographite are mixed as shown in Figure 3.
According to the present invention, the volume density of described negative material is the compacted density of calendering back negative material.The volume density ρ pressure=m/ of described negative material (s * d presses), wherein, m is the total weight of negative material on the negative pole of calendering back, and s is the effective area that calendering back negative material covers negative electrode collector, and d presses the thickness that rolls the back negative electrode material layer for negative pole.In the present invention, difference along with the addition of microparticle electrographite in admixed graphite, the compacted density of admixed graphite also changes thereupon, because native graphite is easy to compacting, then the addition of microparticle electrographite is few more, the content that is native graphite is many more, and the compacted density of negative material just can be big more on the described negative plate.Owing to be key component in the negative electrode active material of the present invention with spherical native graphite, and the advantage of this spherical native graphite is exactly easy compacting, the volume and capacity ratio height, therefore, the pressure of calendering can make the compacted density of negative plate of the present invention reach the 1.65-1.75 gram per centimeter 3To guarantee that battery cathode has high volume energy density, and, because the existence of microparticle flakey electrographite in the admixed graphite, can make the arrangement of native graphite and microparticle flakey electrographite become more tight, therefore in this compacted density scope, spherical native graphite broken phenomenon can not occur, and existing admixed graphite makes the compacted density of negative material can only reach the 1.55-1.60 gram-centimeter 3
Negative pole anticathode adhesive of the present invention has no particular limits, can adopt well known in the art all can be used for the negative pole adhesive of lithium rechargeable battery.Preferred negative pole adhesive is the mixture of hydrophobicity adhesive and hydrophilic adhesive.The ratio of described hydrophobicity adhesive and hydrophilic adhesive is not particularly limited, and can determine according to actual needs, and for example, the part by weight of hydrophilic adhesive and hydrophobicity adhesive can be 0.3: 1-1: 1.Described adhesive can use with the aqueous solution or emulsion form, also can use with solid form, preferably use with the aqueous solution or emulsion form, have no particular limits the concentration of described hydrophilic adhesive solution and the concentration of described hydrophobicity adhesive agent emulsion this moment, the viscosity that can be coated with according to the slurry of positive pole that will prepare and cathode size and the requirement of operability are adjusted flexibly to this concentration, the concentration of for example described hydrophilic adhesive solution can be 0.5-4 weight %, and the concentration of described hydrophobicity adhesive agent emulsion can be 10-80 weight %.Described hydrophobicity adhesive can be polytetrafluoroethylene, butadiene-styrene rubber or their mixture.Described hydrophilic adhesive can be hydroxypropyl methylcellulose, sodium carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol or their mixture.In described adhesive preferably polyethylene alcohol, polytetrafluoroethylene, CMC and the butadiene-styrene rubber one or more.The content of described adhesive is the 0.01-8 weight % of negative electrode active material, is preferably 1-5 weight %.
Described 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.
Negative pole of the present invention can also contain conductive agent, described conductive agent is not particularly limited, can be the cathode conductive agent of this area routine, such as in ketjen carbon black, acetylene black, furnace black, carbon fiber VGCF, conductive carbon black and the electrically conductive graphite one or more.With the negative electrode active material is benchmark, and the content of described conductive agent is 1-15 weight %, is preferably 2-10 weight %.
The preparation method of battery cathode provided by the invention comprises that the slurry that will contain negative material applies and/or is filled on the collector body, dry, calendering, described negative material comprises negative electrode active material and negative pole adhesive, described negative electrode active material is the admixed graphite of native graphite and electrographite, wherein, described native graphite is spherical native graphite, described electrographite is a microparticle flakey electrographite, the particle diameter of described spherical native graphite is greater than the particle diameter of microparticle flakey electrographite, the median particle diameter D of described spherical native graphite and microparticle flakey electrographite 50Difference is the 4-25 micron; The median particle diameter D of described microparticle flakey electrographite 50Be the 0.3-6 micron; The weight ratio of described spherical native graphite and microparticle flakey electrographite is 1: 0.05-0.2.
Prepare negative pole of the present invention, the median particle diameter D of described spherical native graphite 50Be the 10-30 micron, be preferably the 12-25 micron; Microcrystalline coating interplanar distance d 002Be the 0.3354-0.3380 nanometer, the specific area that adopts cryogenic nitrogen absorption BET method to obtain is a 0.5-3 rice 2/ gram.The median particle diameter D of described microparticle flakey electrographite 50Be the 0.3-6 micron, be preferably the 0.5-1.8 micron; The microcrystalline coating interplanar distance d of described flakey electrographite 002Be preferably the 0.3354-0.3400 nanometer, the specific area that adopts cryogenic nitrogen absorption BET method to obtain is a 10-25 rice 2/ gram.With described negative electrode active material is benchmark, and the content of described negative pole adhesive is 0.01-8 weight %; Can also contain with the negative electrode active material is benchmark, and content is preferably the conductive agent of 2-10 weight %, and described conductive agent can be selected from one or more in ketjen carbon black, acetylene black, furnace black, carbon fiber VGCF, conductive carbon black and the electrically conductive graphite.
The described slurry that contains the negative material of negative electrode active material and negative pole adhesive can mix negative material and solvent preparation, the solvent that is used to prepare the slurry that contains negative material can be selected from conventional solvent, as being selected from N-methyl pyrrolidone (NMP), N, dinethylformamide (DMF), N, one or more in N-diethylformamide (DEF), methyl-sulfoxide (DMSO), oxolane (THF) and water and the alcohols.The consumption of described solvent can make the slurry with negative material and the preparation of described solvent have viscosity and flowability, can be coated on the described collector body to get final product.In general, be benchmark with the negative electrode active material, the content of described solvent is 30-90 weight %, is preferably 35-85 weight %.The known coated weight that can control described slurry by the thickness of control coating slurry of those skilled in the art; Solvent in the slurry can be removed in follow-up battery step (as drying etc.).The solid content of slurry that obtains is 30-55 weight %.
The same with prior art, the preparation method of described negative pole is included on the negative electrode collector and applies the slurry that contains the conductive agent that negative electrode active material, negative pole adhesive and selectivity contain, drying, and calendering promptly gets negative pole after the cut-parts.Described drying usually under vacuum condition at 50-160 ℃, carry out under preferred 80-150 ℃.Described calendering can be adopted this area rolling condition commonly used, such as the 0.5-3.0 MPa.Described cut-parts are as well known to those skilled in the art, after calendering is finished, cut according to the negative pole size of prepared battery request, obtain negative pole.
Lithium rechargeable battery provided by the invention comprises battery container and is sealed in this battery container interior electrode group and electrolyte; Described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and wherein, described negative pole is a negative pole of the present invention.Because the present invention only relates to the improvement to the prior art lithium ion secondary battery negative pole, therefore other The Nomenclature Composition and Structure of Complexes to lithium rechargeable battery has no particular limits.
For example, anodal consisting of is conventionally known to one of skill in the art, and in general, positive pole comprises collector body and coating and/or is filled in positive electrode on the collector body.Positive electrode collector can be the collector body of being made by any electric conducting material that shows inertia in the lithium-ion electric pool environment of routine, as being aluminium foil, stainless steel foil or nickel foil, shape can be mesh-like or paper tinsel shape, uses aluminium foil as positive electrode collector in specific embodiments of the present invention.Described positive electrode is conventionally known to one of skill in the art, it comprises positive active material, anodal conductive agent and anodal adhesive, described positive active material can be selected from the positive active material of lithium rechargeable battery routine, as a kind of or its mixture: the Li in the 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 can be the anodal conductive agent of this area routine, such as the ketjen carbon black, acetylene black, furnace black, carbon fiber VGCF, one or more in nano-graphite, graphite and the electrically conductive graphite are benchmark with the positive active material, the content of described anodal conductive agent is 0.01-20 weight %, is preferably 0.5-10 weight %.Described anodal adhesive can adopt the adhesive identical with negative pole, the kind of described anodal adhesive and content are conventionally known to one of skill in the art, for example can be selected from polyvinyl alcohol, polytetrafluoroethylene, polyvinylidene fluoride, CMC and the butadiene-styrene rubber one or more.In general, according to the difference of used anodal adhesive kind, be benchmark with the positive active material, the content of described anodal adhesive is 0.5-8 weight %, is preferably 1-5 weight %.
The preparation method of described positive pole can adopt conventional preparation method.For example, the slurry of described positive active material, anodal conductive agent and anodal adhesive and solvent preparation is applied and/or is filled on the described collector body, drying, calendering can obtain described positive pole.The solvent that is used to prepare anode sizing agent of the present invention can be selected from conventional solvent, as being selected from N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols one or more.The consumption of described solvent can make described slurry have viscosity and flowability, can be coated on the described collector body to get final product.In general be benchmark with the positive active material, the content of described solvent is 30-90 weight %, is preferably 45-85 weight %.Wherein, drying, the method for calendering and condition are conventionally known to one of skill in the art.
Described barrier film has electrical insulation capability and liquid retainability energy, is arranged between positive pole and the negative pole, and is sealed in the battery case with positive pole, negative pole and electrolyte.Described barrier film can be the general various barrier films in this area, such as by the nonwoven fabrics of respectively producing the trade mark, the synthetic resin microporous barrier of those skilled in the art in known each manufacturer production, the preferred synthetic resin microporous barrier that adopts, be excellent with polyolefin microporous film again wherein, as in polyethene microporous membrane, microporous polypropylene membrane and the polyethylene polypropylene composite micro porous film one or more, what adopt in specific embodiments of the present invention is polyethylene, polypropylene composite diaphragm paper.
Described electrolyte is this area electrolyte commonly used, as the mixed solution of electrolyte lithium salt and nonaqueous solvents.Electrolyte lithium salt is selected from lithium hexafluoro phosphate (LiPF 6), in lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and the fluorocarbon based sulfonic acid lithium one or more.Organic solvent can be selected from chain acid esters and ring-type acid esters mixed solution, wherein the chain acid esters can be fluorine-containing for dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other, sulfur-bearing or contain at least a in the chain organosilane ester of unsaturated bond.The ring-type acid esters can (γ-BL), sultone and other be fluorine-containing, sulfur-bearing or contain at least a in the ring-type organosilane ester of unsaturated bond for ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton.In the described electrolyte, the concentration of electrolyte lithium salt is generally the 0.1-2 mol, is preferably the 0.8-1.2 mol.
Unless stated otherwise, all kinds of solvents of the present invention and reagent are commercially available analytical reagent.
Below will the present invention is described further by specific embodiment.
Embodiment 1
Present embodiment illustrates negative pole provided by the invention and preparation method thereof and comprises the battery of this negative pole.
(1) preparation of negative pole
With spherical native graphite (the safe energy in Qingdao company commodity, median particle diameter D 50Be 17.54 microns, microcrystalline coating interplanar distance d 002Corrected value is 0.33650 nanometer, and the specific area that adopts cryogenic nitrogen absorption BET method to obtain is 2.2 meters 2/ gram) with microparticle flakey electrographite (Changsha Xing Cheng company commodity, median particle diameter D 50Be 4.6 microns, microcrystalline coating interplanar distance d 002Corrected value is 0.33784 nanometer, and the specific area that adopts cryogenic nitrogen absorption BET method to obtain is 11.95 meters 2/ gram) carry out abundant mechanical mixture with 1: 0.2 weight ratio and obtain admixed graphite after evenly, stand-by.
The mixture of the above-mentioned admixed graphite of 100 grams, 1.5 gram adhesive polytetrafluoroethylene (PTFE)s and 1.5 gram carboxymethyl celluloses (CMC) is joined in the 100 gram water, in de-airing mixer, stir then and form uniform cathode size.
This slurry is coated on equably on the both sides of Copper Foil, then 90 ℃ of down oven dry, calendaring molding under 2.0 MPa pressure cuts to make and is of a size of 395 * 41 millimeters negative pole, and the volume density of the negative material of this negative pole is 1.70 gram per centimeters 3, wherein contain 2.6 gram active component admixed graphite on this negative plate.
(2) Zheng Ji preparation
With the anodal active component LiCoO of 100 grams 2, 2 gram adhesive vinylidene fluorides (PVDF), 3 gram conductive agent acetylene blacks mixtures join in the 40 gram N-N-methyl-2-2-pyrrolidone N-s (NMP), in de-airing mixer, 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
To include in after positive pole, polypropylene/polyethylene/polypropylene (Celgard) diaphragm paper, negative pole lamination successively and the winding in 4.0 millimeters * 34 millimeters * 46 millimeters the square aluminum hull.
To contain 1 mole lithium hexafluoro phosphate (LiPF 6) ethylene carbonate: the Methylethyl carbonic ester: diethyl carbonate (EC/EMC/DEC) volume ratio be 1: 1: 1 electrolyte about 2.4 the gram, inject above-mentioned battery, and ageing in a conventional manner, the sealed cell aluminum hull can obtain lithium rechargeable battery A1 of the present invention.The design capacity of this battery is 750 MAHs.
Comparative Examples 1
Negative pole of this Comparative Examples explanation prior art and preparation method thereof and the reference cell that comprises this negative pole.
Prepare negative pole and comprise the battery of this negative pole according to the method for embodiment 1, different is, when the preparation battery cathode, used negative electrode active material is that (Qingdao is safe can company's commodity, median particle diameter D for the spherical native graphite of 100 grams 50Be 17.54 microns, microcrystalline coating interplanar distance d 002Corrected value is 0.33650 nanometer, and the specific area that adopts cryogenic nitrogen absorption BET method to obtain is 2.2 meters 2/ restrain), it is 1.6 gram per centimeters that calendering makes the volume density of the negative material of gained negative pole 3, contain 2.6 gram negative electrode active material native graphites on this negative plate.Obtain reference cell AC1.
Comparative Examples 2
Negative pole of this Comparative Examples explanation prior art and preparation method thereof and the reference cell that comprises this negative pole.
Prepare negative pole and comprise the battery of this negative pole according to the method for embodiment 1, different is that when the preparation battery cathode, used negative electrode active material is 100 gram microparticle flakey electrographite (Changsha Xing Cheng company commodity, median particle diameter D 50Be 4.6 microns, microcrystalline coating interplanar distance d 002Corrected value is 0.33784 nanometer, and the specific area that adopts cryogenic nitrogen absorption BET method to obtain is 11.95 meters 2/ restrain), it is 1.6 gram per centimeters that calendering makes the volume density of the negative material of gained negative pole 3, contain 2.6 gram negative electrode active material electrographites on this negative plate.Obtain reference cell AC2.
Comparative Examples 3
Negative pole of this Comparative Examples explanation prior art and preparation method thereof and the reference cell that comprises this negative pole.
Prepare negative pole and comprise the battery of this negative pole according to the method for embodiment 1, different is that when the preparation battery cathode, the weight ratio of spherical native graphite and microparticle flakey electrographite is 10: 3 in the described negative electrode active material; It is 1.6 gram per centimeters that calendering makes the volume density of the negative material of gained negative pole 3, contain 2.6 gram negative electrode active material admixed graphite on this negative plate.Obtain reference cell AC3.
Comparative Examples 4
Negative pole of this Comparative Examples explanation prior art and preparation method thereof and the reference cell that comprises this negative pole.
Prepare negative pole and comprise the battery of this negative pole according to the method for embodiment 1, different is, when the preparation battery cathode, described negative electrode active material is that (Qingdao is safe can company's commodity, median particle diameter D for described spherical native graphite 50Be 17.54 microns, microcrystalline coating interplanar distance d 002Corrected value is 0.33650 nanometer, and the specific area that adopts cryogenic nitrogen absorption BET method to obtain is 2.2 meters 2/ gram) and the admixed graphite of another kind of electrographite, the median particle diameter D of this electrographite 50Be 16.5 microns, microcrystalline coating interplanar distance d 002Corrected value is 0.3365 nanometer, and the specific area that adopts cryogenic nitrogen absorption BET method to obtain is 4.2 meters 2/ gram; The weight ratio of described spherical native graphite and this electrographite is 10: 2.It is 1.6 gram per centimeters that calendering makes the volume density of the negative material of gained negative pole 3, contain 2.6 gram negative electrode active material admixed graphite on this negative plate.Obtain reference cell AC4.
Comparative Examples 5
Negative pole of this Comparative Examples explanation prior art and preparation method thereof and the reference cell that comprises this negative pole.
Prepare negative pole and comprise the battery of this negative pole according to the method for embodiment 1, different is, when the preparation battery cathode, (weight ratio through coating modification native graphite and Delanium is 30: 70 to the negative electrode active material that described negative electrode active material obtains for the method according to the disclosed embodiment 2 of CN1702892A, wherein, through the median particle diameter D of coating modification native graphite 50Be 5 microns, the median particle diameter D of Delanium 50It is 2 microns).It is 1.6 gram per centimeters that calendering makes the volume density of the negative material of gained negative pole 3, contain 2.6 gram negative electrode active material native graphites on this negative plate.Obtain reference cell AC5.
Embodiment 2-7
This embodiment illustrates negative pole provided by the invention and preparation method thereof and comprises the battery of this negative pole.
Prepare negative pole respectively and comprise the battery A2-A7 of this negative pole according to the method for embodiment 1, different is the proportioning of negative electrode active material and median particle diameter D 50, as shown in table 1 below.
Table 1
Figure A20061016111300191
Embodiment 8-14
The lithium ion battery A1-A7 that embodiment 1-7 is made carries out the test of battery capacity, cycle performance, multiplying power discharging property and the performance of overcharging respectively.
(1) battery capacity test
The battery A1-A7 that the foregoing description 1-7 is made carries out the battery capacity test respectively.Test environment is normal temperature, relative humidity 25-85%, and assay method is as follows:
Under 25 ℃, use BS-9300 (R) secondary cell device for detecting performance, charge the battery to 4.2V with the electric current of 0.5C, shelved 5 minutes, and then with the current discharge of 1C to 3.0V, record the discharge capacity of battery thus.The result is as shown in table 2 below.
(2) cycle performance test
Under 25 ℃ of conditions, the battery A1-A7 that embodiment 1-7 is made respectively with the 1C current charges to 4.2V, with constant-potential charge, cut-off current is 0.05C after voltage rises to 4.2V, shelves 10 minutes; Again with the 1C current discharge to 3.0V, shelved 5 minutes.Repeat above step 400 time, obtain the capacity of 400 circulation backs of battery 1C current discharge to 3.0V, 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 2 below.
(3) multiplying power discharging property test
Battery capacity measured in the battery capacity test with method of testing (1) is as normal capacity.Under 25 ℃, the battery A1-A7 that embodiment 1-7 is made is placed on test respectively cashier's office in a shop, earlier carried out constant-current constant-voltage charging 2.5 hours with 0.5C, be limited to 4.2 volts in the charging, after shelving 20 minutes, be discharged to 3.0 volts with the electric current of 1C, 2C and 3C from 4.2 volts respectively, with the 0.5C discharge capacity as 100% o'clock capacity; The ratio of discharge capacity when writing down and calculating respectively with the 0.5C discharge, that is:
C 1C/ C 0.5C: the electric current with 1C is discharged to the discharge capacity of 3.0V and the ratio that is discharged to the discharge capacity of 3.0V with the electric current of 0.5C from 4.2V from 4.2V;
C 2C/ C 0.5C: the electric current with 2C is discharged to the discharge capacity of 3.0V and the ratio that is discharged to the discharge capacity of 3.0V with the electric current of 0.5C from 4.2V from 4.2V;
C 3C/ C 0.5C: the electric current with 3C is discharged to the discharge capacity of 3.0V and the ratio that is discharged to the discharge capacity of 3.0V with the electric current of 0.5C from 4.2V from 4.2V.
(4) over-charging test
The battery A1-A7 that embodiment 1-7 is made charged 24 hours with the electric current of constant voltage 5V, 1A respectively, observed the variation of battery.If battery except that shell expands, the swell, phenomenon such as do not blast, on fire, leakage and impression split, then thinking can be by overcharging experiment, battery quality is qualified, otherwise think can not be by overcharging experiment, battery quality is defective.
Comparative Examples 6-10
The reference lithium ion battery AC1-AC5 that Comparative Examples 1-5 is made carries out the test of battery capacity, cycle performance, multiplying power discharging property and over-charging respectively.
Adopt the method identical with embodiment 8-14 to measure, different is that the battery of measuring is reference lithium ion battery AC1-AC5.The result is as shown in table 2 below.
Table 2
Figure A20061016111300221
By the data in the table 2 as can be seen, the initial discharge capacity of the battery A1-A7 that is prepared by negative pole provided by the invention all more than 755 MAHs, all reaches the requirement of design capacity 750 MAHs; Capability retentions are all more than 86% after 400 circulations; For heavy-current discharge performance, C 1C/ C 0.5CAll at (the general requirement is 95%) more than 97%, C 2C/ C 0.5CAll at (the general requirement is 80%) more than 84%, C 3C/ C 0.5CAll (the general requirement is 50%) more than 63%; And all smooth experiment test that overcharges by 5V, 1A.Especially battery A2, A3 and the A6 that is prepared by embodiment 2,3 and 6 shows more good comprehensive performances.
The reference cell AC1 that obtains with Comparative Examples 1 compares, though the capacity of this battery is higher,, because its negative electrode active material all is spherical native graphite, therefore, worsen serious at 400 circulation back battery performances, in addition, in the test of overcharging, also there are serious problems.
The reference cell AC2 that obtains with Comparative Examples 2 compares, because the negative electrode active material of this battery all is an electrographite, so the battery initial capacity is low.
The reference cell AC3-AC5 that obtains with Comparative Examples 3-5 compares, though their negative electrode active material is the admixed graphite of native graphite and electrographite, and, there is the low problem of capacity in battery AC3; The cycle performance of battery AC4 is relatively poor, and fails smoothly by overcharging test; Because the content of native graphite is low in the negative material of AC5, so compacted density is low, cell thickness is blocked up, and the initial capacity of battery is low excessively.This shows that in the reference cell that is obtained by Comparative Examples 1-5, the neither one battery has high power capacity, good circulation performance and big multiplying power discharging property simultaneously, therefore, the combination property of battery is poor.
In addition, in the over-charging experiment, battery out of the ordinary in the Comparative Examples occurs that battery swell, impression are split, leakage, even blast and phenomenon on fire, therefore can't pass through this experiment smoothly, security performance also has problems, and battery provided by the invention is except the battery container microdilatancy, without any other obvious phenomenon, and can be very smoothly by overcharging test, therefore explanation, battery of the present invention has good security performance.
In sum, lithium rechargeable battery provided by the invention is guaranteeing that battery has under the situation of high power capacity, has excellent cycle performance, big multiplying power discharging property and security performance simultaneously, and the combination property of battery is good.

Claims (10)

1. the negative pole of a lithium rechargeable battery, this negative pole comprises collector body and coating and/or is filled in negative material on this collector body, described negative material comprises negative electrode active material and negative pole adhesive, described negative electrode active material is the mixture of native graphite and electrographite, it is characterized in that, described native graphite is spherical native graphite, described electrographite is a microparticle flakey electrographite, the particle diameter of described spherical native graphite is greater than the particle diameter of microparticle flakey electrographite, the median particle diameter D of described spherical native graphite and microparticle flakey electrographite 50Difference is the 4-25 micron; The median particle diameter D of described microparticle flakey electrographite 50Be the 0.3-6 micron; The weight ratio of described spherical native graphite and microparticle flakey electrographite is 1: 0.05-0.2.
2. negative pole according to claim 1, wherein, the median particle diameter D of described spherical native graphite 50Be the 10-30 micron, the median particle diameter D of described microparticle flakey electrographite 50Be the 0.5-1.8 micron.
3. negative pole according to claim 1 and 2, wherein, the weight ratio of described spherical native graphite and microparticle flakey electrographite is 1: 0.05-0.15.
4. negative pole according to claim 1 and 2, wherein, the compacted density of described negative material is the 1.65-1.75 gram per centimeter 3
5. negative pole according to claim 1 and 2, wherein, the microcrystalline coating interplanar distance d of described microparticle flakey electrographite 002Be the 0.3354-0.3400 nanometer, the specific area that adopts cryogenic nitrogen absorption BET method to obtain is a 10-25 rice 2/ gram; The microcrystalline coating interplanar distance d of described spherical native graphite 002Be the 0.3354-0.3380 nanometer, the specific area that adopts cryogenic nitrogen absorption BET method to obtain is a 0.5-3 rice 2/ gram.
6. the preparation method of the described negative pole of claim 1, this method comprises that the slurry that will contain negative material applies and/or is filled on the collector body, dry, calendering, described negative material comprises negative electrode active material and negative pole adhesive, described negative electrode active material is the mixture of native graphite and electrographite, it is characterized in that, described native graphite is spherical native graphite, described electrographite is a microparticle flakey electrographite, the particle diameter of described spherical native graphite is greater than the particle diameter of microparticle flakey electrographite, the median particle diameter D of described spherical native graphite and microparticle flakey electrographite 50Difference is the 4-25 micron; The median particle diameter D of described microparticle flakey electrographite 50Be the 0.3-6 micron; The weight ratio of described spherical native graphite and microparticle flakey electrographite is 1: 0.05-0.2.
7. method according to claim 6, wherein, the median particle diameter D of described spherical native graphite 50Be the 10-30 micron, the median particle diameter D of described microparticle flakey electrographite 50Be the 0.5-1.8 micron; The weight ratio of described spherical native graphite and microparticle flakey electrographite is 1: 0.05-0.15.
8. according to claim 6 or 7 described methods, wherein, the microcrystalline coating interplanar distance d of described microparticle flakey electrographite 002Be the 0.3354-0.3400 nanometer, the specific area that adopts cryogenic nitrogen absorption BET method to obtain is a 10-25 rice 2/ gram; The microcrystalline coating interplanar distance d of described spherical native graphite 002Be the 0.3354-0.3380 nanometer, the specific area that adopts cryogenic nitrogen absorption BET method to obtain is a 0.5-3 rice 2/ gram.
9. method according to claim 6, wherein, the slurry that contains negative material is the slurry that contains negative material and solvent, the 0.01-8 weight % that described negative pole adhesive consumption is described negative electrode active material, and described solid content of slurry is 30-55 weight %.
10. lithium rechargeable battery, this battery comprise battery container and are sealed in electrode group and electrolyte in this battery container; Described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, it is characterized in that, described negative pole is any described negative pole among the claim 1-5.
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