Patent Grant
9728816
The Present Application claims priority to Chinese Patent Application No. CN 201310113698.3 filed on Apr. 2, 2013, the content of which is fully incorporated in its entirety herein.
The present disclosure relates to a lithium-ion battery, and more specifically to a lithium-rich electrode plate of a lithium-ion battery and a preparation method thereof.
In 1991, Sony Corporation in Japan creatively used carbon material as an anode active material of a lithium-ion battery, which brought a revolutionary change to the lithium-ion battery field. Because the lithium-ion battery has many advantages, such as high voltage, small volume, light weight, high specific energy, non-memory effect, non-pollution, small self-discharge and long cycle life and the like, it has been unprecedentedly developed in application of the field of mobile devices, including mobile phones, cameras, notebook computers and other portable electrical appliances. Since twenty-first century, awareness of environmental protection of the human being has been further improved, so that the lithium-ion battery has more potential to be used, and is generally considered as a desirable power supply of mobile appliances, power supply of electric vehicles and storage device of storage power stations in the new century.
But with a trend of miniaturization and longstanding of portable electronic devices, high energy density of the lithium-ion battery for these devices is required greatly, therefore an active material with high specific capacity is applied to the lithium-ion battery field, wherein alloy material is more outstanding one. For the anode active materials, a Solid Electrolyte Interface membrane (SEI membrane) would be formed during the first charging, which consumes a part of lithium ions deintercalated from the cathode active material, eventually resulting in the first coulombic efficiency of the cell less than 100%. For example, the first coulombic efficiency of graphite material is about 90%, while the alloy anode material is much lower, such as silicon anode active material, the first coulombic efficiency of which ranges from 65% to 85%. In order to improve energy density of the cell, the first coulombic efficiency of the cell is required to increase.
In order to obtain a lithium-rich electrode plate improving the first coulombic efficiency of the cell, domestic and oversea experts have carried out extensive researches, and achieved some achievements. Chinese patent application publication No. CN1830110A discloses a lithium-rich electrode plate with details as follows: lithium metal, an anode material and a non-aqueous liquid are mixed to form a slurry, the slurry is coated on a collector, and then the slurry is baked to obtain a lithium-rich electrode plate of a lithium-ion battery, wherein lithium metal particles are mixed into the coating layer. Due to lithium metal present in the coating layer of the electrode plate, the density of the active material in the electrode plate is lowered, connection among active material particles is weakened and electronic resistance is increased; at the same time, although this method can work in lithium-supplement and finally achieve the object of improving the first coulombic efficiency of the cell, the whole production process of the cell must be operated in a drying chamber and meanwhile the lithium metal and the anode material are difficult to be mixed together, thus the production cost is relative high. Chinese patent application publication No. CN1177417A discloses a lithium-rich lithium ion battery with details as follows: a lithium sheet is covered on a surface of an anode electrode plate, and then wound to form a battery; and then an electrolyte is injected, to produce a lithium-rich lithium-ion battery. When applying this method for lithium-supplement, since relative thin lithium metal sheet can not be produced by the existing technology, the quantity of lithium which can be absorbed by the anode electrode plate is much less than that provided by the lithium metal sheet, which results in problems, such as over lithium-supplement, deposition of lithium in the cell, poor cycle performance, and the like.
Therefore, it is necessary to provide a lithium-rich electrode plate of a lithium-ion battery and a preparation method thereof which can effectively control lithium-supplemental quantity to an anode and improve lithium-supplemental uniformity.
In view of the problems existing in the background technology, an object of the present disclosure is to provide a lithium-rich electrode plate of a lithium-ion battery and a preparation method thereof, which can accurately control lithium-supplemental quantity to an anode.
Another object of the present disclosure is to provide a lithium-rich electrode plate of a lithium-ion battery and a preparation method thereof, which can improve lithium-supplemental uniformity to an anode to produce a lithium-ion battery having good electrochemical performances.
In order to achieve the above objects, in a first aspect of the present disclosure, the present disclosure provides a lithium-rich electrode plate of a lithium-ion battery, comprising: a collector; a film containing an active material and forming on the collector, and forming an elementary electrode plate together with the collector; and a porous lithium sheet covering on the film, wherein a resulting capacity of the porous lithium sheet matches a planned lithium-supplemental capacity to an anode.
In a second aspect of the present disclosure, the present disclosure provides a preparation method of a lithium-rich electrode plate of a lithium-ion battery, for preparing the lithium-rich electrode plate of the lithium-ion battery according to the first aspect of the present disclosure, which comprises steps of: preparing a slurry from an active material, a conductive agent, an adhesive and a solvent, then coating the slurry on a collector, and performing baking to obtain an elementary electrode plate, wherein the slurry coated on the collector becomes a film after baking; making holes on a lithium metal sheet to obtain a porous lithium sheet, wherein a resulting capacity of the porous lithium sheet matches a planned lithium-supplemental capacity to an anode; and covering the porous lithium sheet on a surface of the film of the elementary electrode plate to obtain the lithium-rich electrode plate of the lithium-ion battery.
The present disclosure has following beneficial effects:
The lithium-rich electrode plate of the lithium-ion battery provided by the present disclosure not only overcomes a problem that the conventional lithium-rich electrode plate (wherein a whole lithium sheet without holes is used) yields redundant lithium supplemental capacity to the anode, but also can accurately control lithium-supplemental quantity to the anode, meanwhile can improve lithium-supplemental uniformity and effectively improve the first coulombic efficiency of the lithium-ion battery using the lithium-rich electrode plate, thereby improving energy density of the lithium-ion battery greatly, and ensuring a better electrochemical performance of the lithium-ion battery. The porous lithium sheet provided can increase the gap between an anode layer and a cathode layer of the cell of the lithium-ion battery, improve an entry velocity of the electrolyte, and decrease deformation of the cell. The preparation method of the lithium-rich electrode plate of the lithium-ion battery of the present disclosure can be performed simply and the cost thereof is low.
Hereinafter a lithium-rich electrode plate of a lithium-ion battery and a preparation method thereof and embodiments according to the present disclosure are described in details.
Firstly a lithium-rich electrode plate of a lithium-ion battery according to a first aspect of the present disclosure is described.
A lithium-rich electrode plate of a lithium-ion battery according to a first aspect of the present disclosure comprises: a collector; a film containing an active material and forming on the collector, and forming an elementary electrode plate together with the collector; and a porous lithium sheet covering on the film, wherein a resulting capacity of the porous lithium sheet matches a planned of lithium-supplemental capacity to an anode.
In the lithium-rich electrode plate of the lithium-ion battery according to the present disclosure, the lithium-supplemental quantity to the anode can be accurately controlled through the porous lithium sheet. Meanwhile it should be noted that, the resulting capacity of the porous lithium sheet matching the planned lithium-supplemental capacity to the anode means that the resulting capacity of the porous lithium sheet may be equal to or not equal to the planned lithium-supplemental capacity to the anode. When the resulting capacity of the porous lithium sheet is equal to the planned lithium-supplemental capacity to the anode, it is referred to as a full lithium-supplement. When the resulting capacity of the porous lithium sheet is greater than the planned lithium-supplemental capacity to the anode, it is referred to as an overmuch lithium-supplement. When the resulting capacity of the porous lithium sheet is less than the planned lithium-supplemental capacity to the anode, it is referred to as an insufficient lithium-supplement. In addition, the porous lithium sheet can achieve uniform lithium-supplement to the anode. Furthermore, when a cell is prepared by using the lithium-rich electrode plate, the porous lithium sheet provided increases a gap between an anode layer and a cathode layer of the cell of the lithium-ion battery, the holes in the porous lithium sheet improve an entry velocity of the electrolyte. Both the gap and the holes in the porous lithium sheet can decrease deformation of the cell.
Preferably, in the lithium-rich electrode plate of the lithium-ion battery according to the first aspect of the present disclosure, a thickness of the porous lithium sheet is 1 μm˜500 μm, preferably 10 μm˜50 μm.
Preferably, in the lithium-rich electrode plate of the lithium-ion battery according to the first aspect of the present disclosure, a width of the porous lithium sheet is a, a width of the elementary electrode plate is b, wherein b−40 μm≦a≦b, preferably b−20 μm≦a≦b.
In the lithium-rich electrode plate of the lithium-ion battery according to the first aspect of the present disclosure, a shape of a hole of the porous lithium sheet is at least one of circle, square, rhombus, oval, triangle or polygon.
In the lithium-rich electrode plate of the lithium-ion battery according to the first aspect of the present disclosure, an equivalent aperture of the hole of the porous lithium sheet is 0.10 μm˜20.99 μm, preferably 1.13 μm˜11.28 μm. Herein, the equivalent aperture is calculated as follows: one hole in the porous lithium sheet is presented, an area of the hole is calculated, a diameter as a homalographic circle is then calculated and the calculated diameter is the equivalent aperture.
In the lithium-rich electrode plate of the lithium-ion battery according to the first aspect of the present disclosure, preferably, the holes of the porous lithium sheet are identical and are arranged with equal-interval.
In the lithium-rich electrode plate of the lithium-ion battery according to the first aspect of the present disclosure, the porous lithium sheet has a net structure.
In the lithium-rich electrode plate of the lithium-ion battery according to the first aspect of the present disclosure, the elementary electrode plate may be an elementary anode electrode plate; the active material contained in the film of the elementary electrode plate is an anode active material which is at least one of graphite, silicon or silicon-carbon alloy.
In the lithium-rich electrode plate of the lithium-ion battery according to the first aspect of the present disclosure, the elementary electrode plate is an elementary cathode electrode plate; the active material contained in the film of the elementary electrode plate is a cathode active material which is at least one of lithium cobalt oxide, lithium manganese oxide, lithium iron phosphate or lithium tri-element transition metal oxides.
Next a preparation method of a lithium-rich electrode plate of a lithium-ion battery according to a second aspect of the present disclosure is described.
A preparation method of a lithium-rich electrode plate of a lithium-ion battery according to the present disclosure, for preparing the lithium-rich electrode plate of the lithium-ion battery according to the first aspect of the present disclosure, comprises steps of: preparing a slurry from an active material, a conductive agent, an adhesive and a solvent, then coating the slurry on a collector, and performing baking to obtain an elementary electrode plate, wherein the slurry coated on the collector becomes a film after baking; making holes on a lithium metal sheet to obtain a porous lithium sheet, wherein a resulting capacity of the porous lithium sheet matches a planned lithium-supplemental capacity to an anode; and covering the porous lithium sheet on a surface of the film of the elementary electrode plate to obtain the lithium-rich electrode plate of the lithium-ion battery.
Then examples and comparative examples of the lithium-rich electrode plate of the lithium-ion battery according to the present disclosure are described.
A: Preparation of an Elementary Electrode Plate
An active material graphite (wherein a specific capacity of the graphite was 340 mAh/g, the first coulombic efficiency was 91%), an adhesive, a conductive agent, according to a weight ratio of 92:3:5, were mixed with a solvent to form a slurry (wherein the adhesive was PVDF, the conductive agent was conductive carbon black, the solvent was N-methyl-pyrrolidone (NMP)), the slurry was coated on both sides of a copper foil collector with a coating amount of 100 mg/1540 mm2 at each side, then baking was performed, a film was formed, wherein a water content thereof was less than 300 ppm, then after cold pressing, cutting and welding a corresponding tab, an elementary electrode plate with a width of 160 mm was obtained. The elementary electrode plate was an elementary anode electrode plate.
B: Preparation of a Porous Lithium Sheet (for the Film on the Each Side of the Anode Collector)
1) Rich Amount of Lithium of the Lithium-Rich Electrode Plate
C: Preparation of a Lithium-Rich Electrode Plate
It was the same as example 1 except the following:
A: Preparation of an Elementary Electrode Plate
B: preparation of a Porous Lithium Sheet (for the Film on the Each Side of the Anode Collector)
1) Rich Amount of Lithium of the Lithium-Rich Electrode Plate
It was the same as example 1 except the following:
A: Preparation of an Elementary Electrode Plate
B: Preparation of a Porous Lithium Sheet (for the Film on the Each Side of the Anode Collector)
1) Rich Amount of Lithium of a Lithium-Rich Electrode Plate
It was the same as example 3 except the following:
the shape of the holes was square while making holes, a side-length of the square was 10 μm and the equivalent aperture was 11.28 μm based on calculation as a homalographic circle.
It was the same as example 3 except the following:
a shape of the holes was regular hexagon while making holes, a side-length of the regular hexagon was 5 μm and the equivalent aperture was 9.08 μm based on calculation as a homalographic circle.
It was the same as example 1 except the following:
A: Preparation of an Elementary Electrode Plate
B: Preparation of a Porous Lithium Sheet (for the Film on the Each Side of the Anode Collector)
1) Rich Amount of Lithium of the Lithium-Rich Electrode Plate
It was the same as example 6 except the following:
the capacity per unit area of the lithium metal sheet was:
500 μm×3700 mAh/g×0.534 g/cm3=0.9879 mAh/mm2
the percentage of the area of un-punched area to a total area of the lithium metal sheet was:
[(2.237×10−2 mAh/mm2)×100 mm]/[(0.9879 mAh/mm2)×100 mm]×100%=2.26%
A: Preparation of an Elementary Electrode Plate
B: Preparation of a Porous Lithium Sheet (for the Film on the Each Side of the Anode Collector)
1) Rich Amount of Lithium of a Lithium-Rich Electrode Plate
C: Preparation of a Lithium-Rich Electrode Plate
Only performing the step of preparation of an elementary electrode plate (that is, step A) in example 1. The elementary electrode plate prepared may be referred to as a non-lithium-rich electrode plate.
Only performing the step of preparation of an elementary electrode plate (that is, step A) in example 2. The elementary electrode plate prepared may be referred to as a non-lithium-rich electrode plate.
Only performing the step of preparation of an elementary electrode plate (that is, step A) in example 3. The elementary electrode plate prepared can be referred to as a non-lithium-rich electrode plate.
It was the same as example 3 only except the followings:
a shape of the holes was square while making holes, a side-length of the square was 30 μm and an equivalent aperture was 33.84 μm based on calculation as a homalographic circle.
Only performing the step of preparation of an elementary electrode plate (that is, step A) in example 6. The elementary electrode plate prepared can be referred to as a non-lithium-rich electrode plate.
Hereinafter lithium-ion batteries prepared based on examples 1-8 and comparative examples 1-5, and testing results concerning performances thereof, are presented.
Preparation of cathode electrode plates (corresponding to examples 1-7 and comparative examples 1-5): the elementary electrode plate (that is, the elementary cathode electrode plate) prepared in the step A of example 8 was used as the cathode electrode plate of the examples 1-7 and the comparative examples 1-5.
Preparation of an anode electrode plate (corresponding to example 8): the elementary electrode plate (that is, the elementary anode electrode plate) prepared in the step A of example 3 was used as the anode electrode plate of example 8.
Preparation of lithium-ion batteries: the lithium-rich electrode plates in examples 1-8 and comparative example 4, the non-lithium-rich electrode plates in comparative examples 1-3 and comparative example 5 were wound with dried separators and counter electrode plates to prepare bare cells, after casing the bare cells, injecting electrolyte (wherein the concentration of lithium salt LiPF6 was 1 mol/L, the proportion of other components ethylene carbonate (EC), diethyl carbonate (DEC), vinylene carbonate (VC) and 1,3-propane sultone (PS) was 40:60:1:3), standing by the bare cells in condition of 25° C. to achieve excellent electrolyte infiltration, formation (formation capacity was ICC0), clamp-baking and degassing, finally lithium-ion batteries with lithium-rich cells were obtained.
Capacity testing: After standing by 3 min in a condition of 35° C., the lithium-ion batteries of examples 1-8 and comparative examples 1-5 were charged and discharged as follows: charged to 4.2V at a constant current of 0.5 C, then charged to 0.05 C at the constant voltage of 4.2V, to obtain a charging capacity of AgC0; standing by 3 min; then discharged to 3.0V at a constant current of 0.5 C, to obtain a first discharging capacity of D0; standing by 3 min, finally capacity testing was finished.
A formula for calculating a first coulombic efficiency of cells was D0/(ICC0+AGC0), wherein ICC0+AGC0 was the first charging capacity, the results can be seen in table 1.
(1) Analysis on the Anode Electrode Plates
It can be seen from table 1, both the first discharging capacity D0 and the first coulombic efficiency of the lithium-ion batteries prepared in examples 1-7 were better than those of the lithium-ion batteries prepared in comparative examples 1-5, therefore it was shown that the first coulombic efficiency of the lithium-rich cells prepared by using the lithium-rich electrode plates of the lithium-ion batteries of the present disclosure had an obvious improvement.
The side-length of the square holes in comparative example 4 was 30 μm (the equivalent aperture was 33.84 μm, which was bigger than the equivalent aperture of 20.99 μm), both D0 and the first coulombic efficiency of the lithium-ion battery prepared were obviously worse than those in example 3 and example 4, therefore it was shown that the equivalent aperture of the porous lithium sheet cannot be too big.
The cells of the lithium-ion batteries of examples 1-7 and comparative examples 1-5 were disassembled just after being fully charged at 3.0V, it can be observed that interfacial uniformity of the anode film sheets in examples 1-6 was good, interfacial uniformity of the anode film sheet in example 7 was comparatively worse (After fully charging the battery, there was slight extraction of lithium at the position of lithium-supplement, and the first coulombic efficiency of the battery in example 7 was less than those of the batteries in examples 1-6). It was shown that, if the porous lithium sheet was excessively thick, the percentage of the area of un-punched area to the total area of the lithium metal sheet will be much lower due to the limitation of lithium-supplemental amount, therefore effect of lithium-supplement will be affected because of over-concentration of lithium; interfacial uniformity of the anode film sheet of the cell in comparative example 4 was the worst (after fully charging the battery, there was obvious extraction of lithium at the position of lithium-supplement), it was shown that if the equivalent aperture of the holes made was too big (more than the equivalent aperture of 20.99 μm), the effect of lithium-supplement will be affected because the lithium supplemented cannot achieve uniform diffusion in a short time.
(2) Analysis on the Cathode Electrode Plates
Example 8 and example 3 were compared. The first charging capacity of the cell of the lithium-ion battery in example 8 was obviously higher than that in example 3; the reason was that both the lithium supplemented and the lithium capable of being deintercalated from the cathode itself shall be transferred to the anode during the first charging, when lithium-supplement was performed on the cathode. That is, the first charging capacity comes from the sum of lithium supplemented and lithium provided by the cathode, therefore the first charging capacity was higher than that of the cell without lithium-supplement; meanwhile the first discharging capacity D0 in example 8 was similar to that in example 3, it was shown that the lithium-rich electrode plate of the lithium-ion battery of the present disclosure can improve the discharging capacity of the battery.
In conclusion, the lithium-rich electrode plate of the lithium-ion battery of the present disclosure can avoid excessive lithium-supplement and can achieve uniform lithium-supplement, and can improve the performances of the battery by using the lithium-rich electrode plates, furthermore the preparation process is simple, the cost thereof is low, and it is easy to realize industrial production.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2013 1 0113698 | Apr 2013 | CN | national |
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| 20110165462 | Zhamu | Jul 2011 | A1 |
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| 1177417 | Mar 1998 | CN |
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| Number | Date | Country | |
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| 20140295265 A1 | Oct 2014 | US |
