CN103259002A - Lithium ion battery and electrode plate thereof - Google Patents
Lithium ion battery and electrode plate thereof Download PDFInfo
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- CN103259002A CN103259002A CN2013102036520A CN201310203652A CN103259002A CN 103259002 A CN103259002 A CN 103259002A CN 2013102036520 A CN2013102036520 A CN 2013102036520A CN 201310203652 A CN201310203652 A CN 201310203652A CN 103259002 A CN103259002 A CN 103259002A
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Abstract
The invention discloses a lithium ion battery and an electrode plate thereof. The electrode plate comprises an active substance, wherein lithium ions can be embedded in and separated out of the active substance; the sphericity degree R of the active substance is greater than or equal to 0.89 and smaller than or equal to 0.96; and the median diameter D50 of each active substance particle is 1.0-30 micrometers. The electrode plate is adopted as a positive plate and/or a negative plate by the lithium ion battery. Compared with the prior art, the lithium ion battery has the advantages that a pore channel structure in the electrode plate of the lithium ion battery is improved by means of controlling the sphericity degree of the active substance and the median diameter of each active substance particle, and therefore, the transmission performance of the lithium ions is improved and the purpose of effectively improving the power density of the lithium ion battery is achieved. Meanwhile, by the optimization of the sphericity degree of the active substance in the electrode plate, the isotropy of the lithium ion battery and the stability of the electrode potential of the battery are enhanced, so that the cycling performance of the battery is improved.
Description
Technical field
The invention belongs to the lithium ion battery field, more particularly, the present invention relates to a kind of high power lithium ion cell and electrode slice thereof.
Background technology
Lithium ion battery is extensive day by day in the application in new-energy automobile field, and according to different capacity density and fluence level, the lithium ion battery that electric motor car adopts is divided into HEV, PHEV and BEV three major types usually.Wherein, the power density that HEV requires is the highest, and PHEV takes second place, and BEV is minimum; On the contrary, the energy density that HEV requires is minimum, and PHEV takes second place, and BEV is the highest.In the existing market stage, owing to just be subjected to/the mass-energy density quantitative limitation of negative material own, the energy density of battery is difficult to break through, so the marketization of BEV is also quite preliminary, and HEV and PHEV are then because require low existing ripe market to energy density.As seen, how under the prerequisite that keeps energy content of battery density not reduce, improve the power density of battery, be very important and have the problem of clear and definite practical significance.
In order to address the above problem, many researchers have carried out unremitting research, and have obtained some achievements.Prior art is concluded, found that the technology path that improves the lithium ion battery power density is mainly following four classes: 1) improve the conductivity of electrode active material, as coated with carbon or doping low-valent transition metals lithium ion; 2) conductivity or the consumption of change conductive agent; 3) conductivity of increase electrolyte, the viscosity of reduction electrolyte; 4) thickness of reduction electrode slice.More than several in existing industrialization technology the technology path of widespread usage, really can obviously improve the power density of lithium ion battery, but shortcoming is separately arranged also: as, technology path 1) and 2) through regular meeting because the introducing of non-electrochemical active component, and cause energy content of battery density to reduce, may increase production cost of cells simultaneously; Technology path 4) will inevitably cause the reduction of energy content of battery density; And for route 3), in the lithium-ion electrolyte that existing industrial system is used, common is the mixed solvent system of cyclic ester and ol ester, wherein, the lithium ion of the cyclic ester ability of dissociating is strong, but the viscosity height; A little less than the ability of dissociating of ol ester, but viscosity is low; Therefore, in this a pair of paradox, the conductivity of electrolyte present the downward parabolical form of beginning, and the scope of allotment is very limited along with this allocation process.
In view of this, necessaryly provide a kind of technical scheme that can improve the lithium ion battery power density and not reduce its energy density.
Summary of the invention
The objective of the invention is to: the high power type lithium ion cell and the electrode slice thereof that provide a kind of energy density not reduce.
In order to realize the foregoing invention purpose, the present inventor is through further investigation, sphericity and the particle median particle diameter of finding active material in the electrode slice are bigger to the transmission influence of lithium ion, therefore the sphericity of control electrode material and the cycle performance that the particle median particle diameter can improve lithium ion battery improve its power density.After a large amount of experiments, the power density that has summed up lithium ion battery is relevant with the particle median particle diameter with the sphericity of active material, and its relational expression can be expressed as: P ∝ ε
K*R/ d; Wherein, P is the power density of battery; ε is the porosity of electrode slice; K is constant; R is for being used for constituting the sphericity of electrode slice active material; D is for being used for constituting the median particle diameter of electrode slice active material particle.
Accordingly, the invention provides a kind of lithium ion cell electrode sheet, it comprises the active material that can embed and deviate from lithium ion, and the sphericity R of active material is more than or equal to 0.89 and smaller or equal to 0.96, and the median particle diameter D50 of active material particle is 1.0～30 μ m.
The present invention is defined as the sphericity R of lithium ion cell electrode sheet active material more than or equal to 0.89 and is smaller or equal to 0.96 reason: if the sphericity R of active material is less than 0.89, the inter-granular porosity of the electrode slice that it is made can diminish, even the porosity that makes electrode slice is close to 0, thereby causes the degradation that transports of electrode; Have following defective if the sphericity of active material is too high: 1) active material is in the process of preparation, in order to obtain higher sphericity, especially greater than 0.96 o'clock, often need to carry out strong, long spheroidization processing, this can cause production efficiency to reduce, and manufacturing cost increases; 2) the too high active material of sphericity is in the spheroidization processing procedure, tend to introduce many internal stresss to material, when carrying out cycle charge-discharge after active material is applied in the battery, this internal stress will discharge gradually, cause the fluffy degree of electrode slice to increase, be in contact with one another variation in the electrode slice between the active material, original electron conduction network variation of electrode slice, and then cause the chemical property variation of material; 3) in the operation of rolling of electrode slice, the too high sphericity active material that is distributed in the top layer of electrode slice tends to be crushed, even crushing, expose the crystal face of high reaction activity, after being made into battery, be exposed to the deterioration that high reaction activity crystal face in the electrolyte will cause battery circulation and resistance to elevated temperatures.
The present invention is the reason that the median particle diameter D50 of active material particle is defined as 1.0～30 μ m: the formula that proposes according to the present invention: P ∝ ε
K*R/ d, in theory, the d value should be more low more good.Yet along with the reduction of active material d value, the specific area of material will sharply increase, and namely the surface activity of material strengthens; In lithium-ion battery system, the surface-active enhancing of active material will cause the increase of side reaction, and efficient reduces during initial charge, when battery is worked under higher temperature, may cause the serious flatulence of battery because of the enhancing of side reaction.Similarly, according to above-mentioned formula, more the power of macrocell can be more little for the d value in theory, therefore has a upper limit.
As a kind of improvement of lithium ion cell electrode sheet of the present invention, the median particle diameter D50 of described active material particle is preferably 6～25 μ m.
As a kind of improvement of lithium ion cell electrode sheet of the present invention, the porosity of described electrode slice is 17%～35%.
Described active material particle can be the particle of 1.0～30 μ m for median particle diameter D50, also can be the aggregate bulky grain, and this aggregate bulky grain is made up of granule.Therefore, as a kind of improvement of lithium ion cell electrode sheet of the present invention, the aggregate bulky grain that described active material is made up of granule, short grained median particle diameter D50 are 0.2～2 μ m, the oarse-grained median particle diameter D50 of aggregate is 9～30 μ m, is preferably 9～25 μ m.
As a kind of improvement of lithium ion cell electrode sheet of the present invention, the ratio of the oarse-grained D50 of described aggregate and D90 is 0.1～0.5.
As a kind of improvement of lithium ion cell electrode sheet of the present invention, described electrode slice is electrode film or negative electrode plate, and active material corresponds to positive active material or negative electrode active material.
As a kind of improvement of lithium ion cell electrode sheet of the present invention, it comprises collector and the diaphragm of coating on the collector, contains binding agent, conductive agent and described active material in the diaphragm.
As a kind of improvement of lithium ion cell electrode sheet of the present invention, described conductive agent is one or more in carbon granule, carbon nano-tube, carbon fiber and the Graphene.
The present invention also provides a kind of lithium ion battery, and it comprises electrode film, negative electrode plate, is interval in barrier film and electrolyte between the positive and negative electrode sheet, and one or both in described electrode film and the negative electrode plate are the described electrode slice of above-mentioned arbitrary paragraph.
Compared with prior art, the present invention is by the sphericity of active material and the median particle diameter of particle in the control lithium ion cell electrode sheet, improve the pore passage structure in the electrode slice, and then improved the transmission performance of lithium ion, thereby reached effective purpose of improving the lithium ion battery power density.Simultaneously, the optimization of electrode slice active material sphericity has strengthened the isotropism of lithium ion battery, has improved the stability of battery electrode current potential, thereby has improved the cycle performance of battery.
Description of drawings
Below in conjunction with the drawings and specific embodiments lithium ion battery of the present invention and electrode slice thereof are further elaborated, wherein:
Fig. 1 is the structural representation of lithium ion cell electrode sheet of the present invention.
Fig. 2 is the embodiment of lithium ion battery of the present invention and the discharge energy density comparison diagram of Comparative Examples.
Embodiment
See also Fig. 1, lithium ion cell electrode sheet of the present invention comprises collector 10 and the diaphragm of coating on the collector 10, the active material 16 that contains binding agent 12, conductive agent 14 in the diaphragm and can embed and deviate from lithium ion.
The sphericity of particle and distribute can be directly Sysmex FPIA-3000 by Ma Erwen instrument (Malvern) company record: from the particle suspension liquid that dilutes, take a sample, allow this suspension pass through measuring cell, utilize stroboscopic illumination technology and ccd video camera to catch particle image, again each particle is carried out information extraction, quantize calculating and get final product; Particle grain size and distribute then can be directly Mastersize-2000 and ESEM statistical measurement by Ma Erwen instrument (Malvern) company obtain.
In order to make goal of the invention of the present invention, technical scheme and useful technique effect more clear, below in conjunction with embodiment and accompanying drawing the present invention is described in further detail, but, should be understood that, embodiments of the invention only are in order to explain the present invention, be not in order to limit the present invention, and the embodiments of the invention embodiment that is not limited to provide in the specification.
Embodiment A 1
The making of electrode film: with sphericity R be 0.89, median particle diameter is the active material LiCoO of 14 μ m
2With bonding agent PVDF(Kynoar), the conductive agent conductive black mixes by a certain percentage, obtain finely dispersed anode sizing agent through high-speed stirred, then anode sizing agent is uniformly coated on the aluminium foil, forced air drying obtains porosity and is 21% electrode film after roll-in.
The making of negative electrode plate: with sphericity R be 0.95, median particle diameter is the active material graphite and bonding agent SBR(butadiene-styrene rubber of 15 μ m) and the CMC(sodium carboxymethylcellulose), the conductive agent conductive black mixes by a certain percentage, obtain finely dispersed cathode size through high-speed stirred, then cathode size is uniformly coated on the Copper Foil, forced air drying obtains porosity and is 28% negative electrode plate after roll-in.
The making of lithium ion battery: with the electrode film that makes, negative electrode plate and barrier film are reeled and are assembled into battery, and drying obtains lithium ion battery after dewatering, annotate operations such as electrolyte, encapsulation.
Embodiment A 2
Electrode film: the LiCoO that positive active material adopts Mg to mix
2, its sphericity R is 0.93, median particle diameter is 9 μ m; Conductive agent adopts conductive black; Bonding agent adopts PVDF; Using the method identical with embodiment A 1 to make porosity is 17% electrode film.
Negative electrode plate: negative electrode active material adopts that sphericity R is 0.95, median particle diameter is the graphite of 25 μ m, and bonding agent adopts SBR and CMC, conductive agent to adopt conduction charcoal fiber, and using the method identical with embodiment A 1 to make porosity is 35% negative electrode plate.
Lithium ion battery: use the method identical with embodiment A 1 to make lithium ion battery.
Embodiment A 3
Electrode film: the LiMn that positive active material adopts granule to reunite and form
1/3Ni
1/3Co
1/3O
2, its sphericity R is 0.96, and short grained median particle diameter is 0.5 μ m, and the oarse-grained median particle diameter of reuniting is 17 μ m, and the ratio of the oarse-grained D50 of aggregate and D90 is 0.5; Conductive agent adopts the conduction carbon nanotube; Bonding agent adopts PVDF; Using the method identical with embodiment A 1 to make porosity is 21% electrode film.
Negative electrode plate: negative electrode active material adopts that sphericity R is 0.95, median particle diameter is the graphite of 21 μ m, and bonding agent adopts SBR and CMC, conductive agent to adopt conductive black, and using the method identical with embodiment A 1 to make porosity is 28% negative electrode plate.
Lithium ion battery: use the method identical with embodiment A 1 to make lithium ion battery.
Embodiment A 4
The LiFePO that positive active material adopts granule to reunite and form
4, its sphericity R is 0.96, and short grained median particle diameter is 0.2 μ m, and the oarse-grained median particle diameter of reuniting is 9 μ m, and the ratio of the oarse-grained D50 of aggregate and D90 is 0.1; Conductive agent adopts conductive black; Bonding agent adopts PVDF; Using the method identical with embodiment A 1 to make porosity is 21% electrode film.
Negative electrode plate: negative electrode active material adopts that sphericity R is 0.96, median particle diameter is the graphite of 17 μ m, and bonding agent adopts SBR and CMC, conductive agent to adopt conductive black, and using the method identical with embodiment A 1 to make porosity is 28% negative electrode plate.
Lithium ion battery: use the method identical with embodiment A 1 to make lithium ion battery.
Embodiment A 5
Electrode film: positive active material adopts LiMn
2O
4, its sphericity R is 0.91, median particle diameter is 6 μ m; Conductive agent adopts conductive black; Bonding agent adopts PVDF; Using the method identical with embodiment A 1 to make porosity is 21% electrode film.
Negative electrode plate: negative electrode active material adopts that sphericity R is 0.95, median particle diameter is the graphite of 21 μ m, and bonding agent adopts SBR and CMC, conductive agent to adopt conductive black, and using the method identical with embodiment A 1 to make porosity is 28% negative electrode plate.
Lithium ion battery: use the method identical with embodiment A 1 to make lithium ion battery.
Embodiment A 6
Electrode film: positive active material adopts embodiment A 3 described LiMn
1/3Ni
1/3Co
1/3O
2With embodiment A 5 described LiMn
2O
4Made mixture; Conductive agent adopts the conduction carbon nanotube; Bonding agent adopts PVDF; Using the method identical with embodiment A 1 to make porosity is 21% electrode film.
Negative electrode plate: negative electrode active material adopts that sphericity R is 0.95, median particle diameter is the graphite of 30 μ m, and bonding agent adopts SBR and CMC, conductive agent to adopt conductive black, and using the method identical with embodiment A 1 to make porosity is 28% negative electrode plate.
Lithium ion battery: use the method identical with embodiment A 1 to make lithium ion battery.
Embodiment A 7
Electrode film: positive active material adopts LiCoO
2, its sphericity R is 0.89, median particle diameter is 14 μ m; Conductive agent adopts conductive black; Bonding agent adopts PVDF; Using the method identical with embodiment A 1 to make porosity is 21% electrode film.
Negative electrode plate: the Li that negative electrode active material adopts granule to reunite and form
4Ti
5O
12Its sphericity R is 0.96, short grained median particle diameter is 2 μ m, the oarse-grained median particle diameter of reuniting is 30 μ m, the ratio of the oarse-grained D50 of aggregate and D90 is 0.3, bonding agent adopts PVDF, conductive agent to adopt Graphene, and using the method identical with embodiment A 1 to make porosity is 28% negative electrode plate.
Lithium ion battery: use the method identical with embodiment A 1 to make lithium ion battery.
Embodiment A 8
Electrode film: positive active material adopts LiCoO
2, its sphericity R is 0.89, median particle diameter is 14 μ m; Conductive agent adopts conductive black; Bonding agent adopts PVDF; Using the method identical with embodiment A 1 to make porosity is 21% electrode film.
Negative electrode plate: negative electrode active material adopts that sphericity R is 0.89, median particle diameter is the Si-C alloy of 1 μ m, and bonding agent adopts SBR and CMC, conductive agent to adopt conductive black, and using the method identical with embodiment A 1 to make porosity is 28% negative electrode plate.
Lithium ion battery: use the method identical with embodiment A 1 to make lithium ion battery.
Embodiment B 1
Different with embodiment A 3 is: positive active material is the LiMn that granule is reunited and formed
1/3Ni
1/3Co
1/3O
2, its sphericity R is 0.88, and short grained median particle diameter is 0.5 μ m, and the oarse-grained median particle diameter of reuniting is 17 μ m, and the ratio of the oarse-grained D50 of aggregate and D90 is 0.5, other is identical with embodiment A 3, repeats no more herein.
Embodiment B 2
Different with embodiment A 3 is: positive active material is the LiMn that granule is reunited and formed
1/3Ni
1/3Co
1/3O
2, its sphericity R is 0.96, and short grained median particle diameter is 0.5 μ m, and the oarse-grained median particle diameter of reuniting is 40 μ m, and the ratio of the oarse-grained D50 of aggregate and D90 is 0.5, other are identical with embodiment A 3, repeat no more herein.
Embodiment B 3
Different with embodiment A 3 is: negative electrode active material is graphite, and its sphericity R is 0.69, and median particle diameter is 21 μ m; Other are identical with embodiment A 3, repeat no more herein.
Comparative Examples 1
Different with embodiment A 3 is: positive active material is the LiMn that granule is reunited and formed
1/3Ni
1/3Co
1/3O
2, its sphericity R is 0.88, and short grained median particle diameter is 0.5 μ m, and the oarse-grained median particle diameter of reuniting is 17 μ m, and the ratio of the oarse-grained D50 of aggregate and D90 is 0.5; Negative electrode active material is graphite, and its sphericity R is 0.95, and median particle diameter is 35 μ m; Other are identical with embodiment A 3, repeat no more herein.
Embodiment A 3, A5, A6, Embodiment B 1, B2, B3 and Comparative Examples 1 lithium ion cell prepared are carried out the power density experiment, and the result as shown in Figure 2.As can be seen from Figure 2, embodiment of the invention A3, A5 and A6 and Embodiment B 1, B2 and B3 lithium ion cell prepared power density ratio Comparative Examples 1 obviously improve.The power density formula P ∝ ε that this also sums up with the inventor
K*R/ d matches: the positive active material sphericity of Comparative Examples 1 is lower, and the particle diameter of negative electrode active material is bigger, and therefore for positive plate, under identical bulk density, the porosity that forms after the stacked in multi-layers is lower; For negative plate, the active material that particle diameter is bigger can increase the free path that transports of lithium ion.Therefore Comparative Examples 1 is unfavorable for the performance of power of battery density.On the contrary, embodiment A 3, A5, A6 are because the active material particle degree that adopts is less and sphericity is better, thereby be conducive to reduce the diffusion free path of lithium ion, and the loose structure that is stacked into has good pore passage structure, be conducive to the infiltration of electrolyte and transporting of lithium ion, so battery table has revealed good power density.
Compared with prior art, the present invention is by sphericity and the particle median particle diameter of active material in the control lithium ion cell electrode sheet, improve the pore passage structure in the electrode slice, and then improved the transmission performance of lithium ion, thereby reached effective purpose of improving the lithium ion battery power density.Simultaneously, the optimization of electrode slice active material sphericity has strengthened the isotropism of lithium ion battery, has improved the stability of battery electrode current potential, thereby has improved the cycle performance of battery.It should be noted that, lithium ion cell electrode sheet of the present invention is when improving power of battery density, can not cause the reduction of energy content of battery density, also can not bring the rising of battery manufacturing cost, and the technology path 3 that can mention with technical background) use that combines is with the power density of further raising lithium ion battery.In addition, the present invention also has advantage simple to operate, therefore has broad application prospects.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also carry out suitable change and modification to above-mentioned execution mode.Therefore, the embodiment that discloses and describe above the present invention is not limited to also should fall in the protection range of claim of the present invention modifications and changes more of the present invention.In addition, although used some specific terms in this specification, these terms do not constitute any restriction to the present invention just for convenience of description.
Claims (10)
1. lithium ion cell electrode sheet, it comprises the active material that can embed and deviate from lithium ion, it is characterized in that: the sphericity R of described active material is more than or equal to 0.89 and smaller or equal to 0.96, and the median particle diameter D50 of active material particle is 1.0～30 μ m.
2. lithium ion cell electrode sheet according to claim 1, it is characterized in that: the porosity of described electrode slice is 17%～35%.
3. lithium ion cell electrode sheet according to claim 1, it is characterized in that: the median particle diameter D50 of described active material particle is 6～25 μ m.
4. lithium ion cell electrode sheet according to claim 1, it is characterized in that: the aggregate bulky grain that described active material particle is made up of granule, short grained median particle diameter D50 is 0.2～2 μ m, and the oarse-grained median particle diameter D50 of aggregate is 9～30 μ m.
5. lithium ion cell electrode sheet according to claim 4, it is characterized in that: the oarse-grained median particle diameter D50 of described aggregate is 9～25 μ m.
6. lithium ion cell electrode sheet according to claim 4, it is characterized in that: the ratio of the oarse-grained D50 of described aggregate and D90 is 0.1～0.5.
7. lithium ion cell electrode sheet according to claim 1, it is characterized in that: described electrode slice is electrode film or negative electrode plate, and active material corresponds to positive active material or negative electrode active material.
8. lithium ion cell electrode sheet according to claim 1 is characterized in that: comprise collector and the diaphragm of coating on the collector, contain binding agent, conductive agent and described active material in the diaphragm.
9. lithium ion cell electrode sheet according to claim 8, it is characterized in that: described conductive agent is one or more in carbon granule, carbon nano-tube, carbon fiber and the Graphene.
10. lithium ion battery, it comprises electrode film, negative electrode plate, is interval in barrier film and electrolyte between the positive and negative electrode sheet, it is characterized in that: one or both in described electrode film and the negative electrode plate are each described electrode slice in the claim 1 to 9.
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| CN108328614A (en) * | 2017-12-28 | 2018-07-27 | 合肥国轩高科动力能源有限公司 | One kind is for fast charging type graphite negative material of lithium ion battery and preparation method thereof |
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| CN114597326A (en) * | 2022-03-22 | 2022-06-07 | 珠海冠宇电池股份有限公司 | Negative electrode active material, negative plate containing negative electrode active material and battery |
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| CN114937758A (en) * | 2022-03-22 | 2022-08-23 | 珠海冠宇电池股份有限公司 | Negative electrode active material, negative plate containing negative electrode active material and battery |
| CN115053370A (en) * | 2021-09-28 | 2022-09-13 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
| CN116154103A (en) * | 2023-04-17 | 2023-05-23 | 中创新航科技集团股份有限公司 | Negative plate and lithium ion battery using same |
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