CN118039795A - Lithium ion battery pole piece, preparation method thereof and lithium ion battery - Google Patents
Lithium ion battery pole piece, preparation method thereof and lithium ion battery Download PDFInfo
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- CN118039795A CN118039795A CN202410445005.9A CN202410445005A CN118039795A CN 118039795 A CN118039795 A CN 118039795A CN 202410445005 A CN202410445005 A CN 202410445005A CN 118039795 A CN118039795 A CN 118039795A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 130
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 127
- 230000001502 supplementing effect Effects 0.000 claims abstract description 82
- 239000000463 material Substances 0.000 claims abstract description 77
- 239000007774 positive electrode material Substances 0.000 claims abstract description 24
- 239000007773 negative electrode material Substances 0.000 claims abstract description 12
- 230000002441 reversible effect Effects 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 18
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- 239000010405 anode material Substances 0.000 claims description 8
- 239000006183 anode active material Substances 0.000 claims description 5
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- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000339 iron disulfide Inorganic materials 0.000 claims description 2
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 2
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 13
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the field of batteries, in particular to a lithium ion battery pole piece, a preparation method thereof and a lithium ion battery. The lithium ion battery pole piece comprises: a positive pole piece and a negative pole piece; the positive electrode plate comprises a first current collector, a lithium-free positive electrode material layer and a first lithium supplementing material layer which are sequentially arranged; the negative electrode plate comprises a second current collector, a lithium-free negative electrode material layer and a second lithium supplementing material layer which are sequentially arranged. The lithium ion battery pole piece has the characteristics of long service life and high energy density, and has small volume effect.
Description
Technical Field
The invention relates to the field of batteries, in particular to a lithium ion battery pole piece, a preparation method thereof and a lithium ion battery.
Background
The lithium ion battery is the first choice of consumer electronic batteries and new energy automobile power batteries due to the advantages of high energy density, long cycle life, no memory effect and the like, but the energy density of the current lithium ion battery is limited by a positive electrode material and a negative electrode material, so that the space is further limited.
Carbon fluoride, metal fluoride, elemental sulfur, oxygen and carbon dioxide are used as positive electrode active materials, and have the advantage of high specific capacity, so that the positive electrode active materials are the positive electrode development direction of a lithium battery with high energy density in the future, but all the positive electrode active materials do not contain lithium and need to be matched with a metal lithium negative electrode, and the problems of dendrite growth, continuous side reaction, large volume effect and the like of the metal lithium negative electrode cause the very poor cycle life and safety of the battery using the metal lithium as the negative electrode.
In view of this, the present invention has been made.
Disclosure of Invention
Aiming at the problems of poor safety and short service life caused by the problems of dendrite growth, continuous side reaction, large volume effect and the like of the existing lithium-free positive electrode which is used together with a metal lithium negative electrode, the invention provides a lithium ion battery pole piece, a preparation method thereof and a lithium ion battery.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
One aspect of the invention relates to a lithium ion battery pole piece comprising: a positive pole piece and a negative pole piece;
the positive electrode plate comprises a first current collector, a lithium-free positive electrode material layer and a first lithium supplementing material layer which are sequentially arranged;
the negative electrode piece comprises a second current collector, a lithium-free negative electrode material layer and a second lithium supplementing material layer which are sequentially arranged;
The capacity of the lithium supplementing surfaces of the positive pole piece and the negative pole piece is 30% -80% of the capacity of the reversible surface of the positive pole piece respectively.
The lithium ion battery pole piece has the characteristics of long service life and high energy density, and has small volume effect.
The invention also relates to a preparation method of the lithium ion battery pole piece, which comprises the following steps:
Coating a lithium-free positive electrode material on a first current collector, and performing first drying and first rolling to obtain a positive electrode plate precursor; attaching the lithium supplementing material in the first lithium supplementing material layer on the positive electrode plate precursor to obtain a positive electrode plate;
coating a lithium-free anode material on a second current collector for second drying and second rolling to obtain an anode piece precursor; and attaching the lithium supplementing material in the second lithium supplementing material layer on the anode electrode plate precursor to obtain the anode electrode plate.
The preparation method of the lithium ion battery pole piece is simple and easy to operate, and the prepared lithium ion battery pole piece has the characteristics of long service life and high energy density.
The invention also relates to a lithium ion battery, and the lithium ion battery pole piece prepared by the preparation method of the lithium ion battery pole piece is assembled, dried, injected with liquid and formed.
Compared with the prior art, the invention has the beneficial effects that:
(1) The lithium ion battery pole piece provided by the invention has the characteristics of long service life, high energy density and small volume effect; the positive electrode active material and the negative electrode active material which do not contain lithium are adopted, and the positive electrode plate and the negative electrode plate are provided with lithium supplementing material layers, so that the problems of dendrite growth, continuous side reaction and large volume effect of the metal lithium negative electrode can be avoided.
(2) The preparation method of the lithium ion battery pole piece provided by the invention is simple and easy to operate, and meanwhile, the positive electrode and the negative electrode are subjected to lithium supplementation, so that the problems that full lithium intercalation is difficult to realize and lithium precipitation is easily caused by over-lithiation due to the fact that lithium is only supplemented to the negative electrode are avoided, and the prepared lithium ion battery pole piece has the characteristics of long service life, high energy density and small volume effect.
(3) The lithium ion battery provided by the invention has the advantages that the prepared battery has a full lithium intercalation state, is not easy to over-lithiate and is not easy to precipitate lithium, the service life is long, the energy density is high, and the volume effect is small.
Detailed Description
The technical solution of the present invention will be clearly and completely described in conjunction with the specific embodiments, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
One aspect of the invention relates to a lithium ion battery pole piece comprising: a positive pole piece and a negative pole piece;
the positive electrode plate comprises a first current collector, a lithium-free positive electrode material layer and a first lithium supplementing material layer which are sequentially arranged;
the negative electrode piece comprises a second current collector, a lithium-free negative electrode material layer and a second lithium supplementing material layer which are sequentially arranged;
The lithium supplementing surface capacity of the positive electrode plate and the negative electrode plate is 30% -80% (for example, 30%, 40%, 50%, 60%, 70% or 80%) of the reversible surface capacity of the positive electrode plate respectively. According to the design of the surface capacity of different battery cells, the lithium supplementing amount is dynamically adjusted, side reactions in the lithium supplementing process of the metal lithium are considered, and the specific capacity of the metal lithium is calculated to be 3200mAh/g according to 83%. The above is defined to ensure a sufficiently large negative electrode margin, preventing occurrence of a lithium precipitation problem.
The lithium ion battery pole piece has the characteristics of long service life, high energy density and small volume effect; the positive electrode active material and the negative electrode active material which do not contain lithium are adopted, and the positive electrode plate and the negative electrode plate are provided with lithium supplementing material layers, so that the problems of dendrite growth, continuous side reaction and large volume effect of the metal lithium negative electrode can be avoided.
The reversible capacity refers to the electric quantity which can be stored and released reversibly on the unit electrode area in the charge and discharge process of the battery.
Further, the reversible surface capacity of the negative electrode sheet is 1.02 to 1.15 times (for example, 1.02 times, 1.05 times, 1.08 times, 1.10 times, 1.13 times or 1.15 times) that of the positive electrode sheet.
Further, the thickness of the first lithium supplementing material layer is 8-20 μm.
In some specific embodiments, the thickness of the first lithium-compensating material layer may be, for example, but not limited to, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 16 μm, 18 μm, or 20 μm.
Further, the thickness of the second lithium supplementing material layer is 8-20 μm.
In some specific embodiments, the thickness of the second lithium-compensating material layer may be, for example, but not limited to, 8 μm, 12 μm, 14 μm, 16 μm, 18 μm, 19 μm, or 20 μm.
The thicknesses of the first lithium supplementing material layer and the second lithium supplementing material layer are controlled within a certain range, lithium is easy to separate out if the thickness of the lithium supplementing material layer is too large, and the amount of lithium supplementing is insufficient if the thickness is too small.
Further, the lithium supplementing material in the first lithium supplementing material layer includes: and lithium metal.
Further, the lithium supplementing material in the second lithium supplementing material layer includes: and lithium metal.
The lithium supplementing material layer is prepared by means of metal lithium calendaring and laminating, vapor plating, lithium powder coating and rolling and the like.
Further, the metal lithium related to the invention is pure metal lithium with purity of more than 99.9%.
Further, the lithium-free positive electrode material layer comprises, in parts by mass: 80-97 parts of a lithium-free positive electrode active material, 0.5-18 parts of a conductive agent and 0.5-2 parts of a binder.
In some specific embodiments, the lithium-free positive electrode active material in the lithium-free positive electrode material layer may be, for example, but not limited to, 80, 82, 84, 86, 88, 90, 93, 95, or 97 parts by mass; the conductive agent may be, for example, but not limited to, 0.5 parts, 1 part, 3 parts, 5 parts, 7 parts, 9 parts, 12 parts, 14 parts, 16 parts, or 18 parts; the binder may be, for example, but not limited to, 0.5 parts, 1 part, 1.5 parts, or 2 parts.
Further, the lithium-free positive electrode active material includes: at least one of carbon fluoride, iron trifluoride, titanium disulfide, molybdenum disulfide, iron disulfide, manganese dioxide, elemental sulfur, or vulcanized polyacrylonitrile.
Further, the lithium-free anode material layer comprises the following components in parts by weight: 95-98 parts of lithium-free anode active material, 0.5-2 parts of conductive agent and 0.5-3 parts of binder.
In some specific embodiments, the lithium-free anode active material in the lithium-free anode material layer may be, for example, but not limited to, 95 parts, 96 parts, 97 parts, or 98 parts by mass; the conductive agent may be, for example, but not limited to, 0.5 parts, 0.7 parts, 0.9 parts, 1.1 parts, 1.3 parts, 1.5 parts, 1.7 parts, 1.9 parts, or 8 parts; the binder may be, for example, but not limited to, 0.5, 1, 1.5, 2, or 3 parts.
Further, the lithium-free anode active material includes: graphite, silicon alloy, tin alloy, silicon carbon, silicon oxygen, tin carbon, tin oxygen, soft carbon or hard carbon.
Further, the graphite comprises: artificial graphite and/or natural graphite.
Further, the soft carbon is amorphous carbon graphitizable at high temperatures above 2500 ℃, including in particular but not limited to: at least one of petroleum coke, needle coke, carbon fiber or carbon microsphere.
Further, hard carbon is carbon that is difficult to graphitize at high temperatures above 2500 ℃, including, but not limited to: at least one of resinous carbon, organic polymer pyrolytic carbon, or carbon black.
Further, the silicon alloy and tin alloy according to the present invention are selected from materials conventional in the art.
Further, the conductive agent is selected from conventional conductive agents in the art, including but not limited to: at least one of conductive carbon black, ketjen black, carbon nanotubes, graphene, conductive graphite, or conductive carbon fibers.
Further, the binder is selected from binders conventional in the art, including but not limited to: at least one of polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polypropylene, polyacrylate, polyvinylidene fluoride hexafluoropropylene, sodium carboxymethyl cellulose, styrene butadiene rubber or nitrile butadiene rubber.
The invention also relates to a preparation method of the lithium ion battery pole piece, which comprises the following steps:
Coating a lithium-free positive electrode material on a first current collector, and performing first drying and first rolling to obtain a positive electrode plate precursor; attaching the lithium supplementing material in the first lithium supplementing material layer on the positive electrode plate precursor to obtain a positive electrode plate;
coating a lithium-free anode material on a second current collector for second drying and second rolling to obtain an anode piece precursor; and attaching the lithium supplementing material in the second lithium supplementing material layer on the anode electrode plate precursor to obtain the anode electrode plate.
The preparation method of the lithium ion battery pole piece is simple and easy to operate, and meanwhile, lithium is supplemented to the positive electrode and the negative electrode, so that the problems that full lithium intercalation is difficult to achieve due to lithium supplementation to the negative electrode, and lithium precipitation is easily caused by over-lithiation are avoided, and the prepared lithium ion battery pole piece has the characteristics of long service life, high energy density and small volume effect.
Further, the lithium supplementing material in the first lithium supplementing material layer and the lithium supplementing material in the second lithium supplementing material layer are respectively attached to the positive electrode plate precursor or the negative electrode plate precursor in a rolling manner after being rolled and attached with ultrathin metal lithium, lithium vapor plating and lithium powder coating.
The invention also relates to a lithium ion battery, and the lithium ion battery pole piece prepared by the preparation method of the lithium ion battery pole piece is assembled, dried, injected with liquid and formed.
The lithium ion battery has the advantages of full lithium intercalation, difficult occurrence of over-lithiation, difficult occurrence of lithium precipitation, long service life, high energy density and small volume effect.
Further, the temperature of the drying treatment is 40-100 ℃. The lithium intercalation is completed in the drying process, and the temperature of the drying process determines the lithium intercalation effect.
In some specific embodiments, the temperature of the drying process may be, for example, but not limited to, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, or 100 ℃.
Further, the drying treatment time is 1-24 hours.
In some specific embodiments, the drying process may be performed for a period of time such as, but not limited to, 1h, 3h, 5h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, or 24h.
Further, the drying treatment is performed in vacuum, oxygen, carbon dioxide, argon or helium and other environments to avoid side reactions of metallic lithium and residual nitrogen.
The electrolyte of the lithium ion battery can be a liquid electrolyte system or an all-solid-state semi-solid electrolyte system.
Embodiments of the present invention will be described in detail below with reference to examples.
Example 1
The lithium ion battery pole piece provided in this embodiment includes: a positive pole piece and a negative pole piece;
The positive pole piece comprises a first current collector, a lithium-free positive pole material layer and a first lithium supplementing material layer which are sequentially arranged; the negative electrode plate comprises a second current collector, a lithium-free negative electrode material layer and a second lithium supplementing material layer which are sequentially arranged;
The capacity of the lithium supplementing surface of the positive electrode plate is 36% of the capacity of the reversible surface of the positive electrode plate, and the capacity of the lithium supplementing surface of the negative electrode plate is 68% of the capacity of the reversible surface of the positive electrode plate; the reversible surface capacity of the negative pole piece is 1.10 times of the reversible surface capacity of the positive pole piece;
The thickness of the first lithium supplementing material layer is 10 mu m; the thickness of the second lithium supplementing material layer is 19 mu m; the lithium supplementing materials in the first lithium supplementing material layer and the second lithium supplementing material layer are metal lithium foils;
the lithium-free positive electrode material layer comprises the following components in parts by mass: 90 parts of vulcanized polyacrylonitrile, 7 parts of conductive carbon black (SP), 1 part of Carbon Nano Tube (CNT) and 2 parts of polyvinylidene fluoride (PVDF);
The lithium-free anode material layer comprises the following components in parts by mass: 86 parts of artificial graphite, 10 parts of silica, 1 part of carbon black, 1 part of sodium carboxymethylcellulose and 2 parts of styrene-butadiene latex (SBR).
The preparation method of the lithium ion battery pole piece provided by the embodiment comprises the following steps:
1. uniformly mixing a lithium-free positive electrode material in an N-methyl pyrrolidone (NMP) solvent to prepare slurry, coating the slurry on an aluminum foil with the thickness of 12 microns, drying and rolling to form a positive electrode plate precursor, wherein the single-sided surface density is 8mg/cm 2;
2. Uniformly mixing a lithium-free anode material in an aqueous solution to prepare slurry, coating the slurry on a copper foil with the thickness of 6 microns, drying and rolling to form an anode piece precursor, wherein the single-sided surface density is 8.2mg/cm 2;
3. rolling and attaching a metal lithium sheet on a positive electrode sheet precursor to obtain a positive electrode sheet;
4. and rolling and attaching a metal lithium sheet on the anode electrode sheet precursor to obtain the anode electrode sheet.
Example 2
The lithium ion battery pole piece provided in this embodiment includes: a positive pole piece and a negative pole piece;
The positive pole piece comprises a first current collector, a lithium-free positive pole material layer and a first lithium supplementing material layer which are sequentially arranged; the negative electrode plate comprises a second current collector, a lithium-free negative electrode material layer and a second lithium supplementing material layer which are sequentially arranged;
The capacity of the lithium supplementing surfaces of the positive pole piece and the negative pole piece is 30% of the capacity of the reversible surface of the positive pole piece respectively; the reversible surface capacity of the negative pole piece is 1.10 times of the reversible surface capacity of the positive pole piece;
the thickness of the first lithium supplementing material layer is 8 mu m; the thickness of the second lithium supplementing material layer is 20 mu m; the lithium supplementing materials in the first lithium supplementing material layer and the second lithium supplementing material layer are metal lithium foils;
Otherwise, the same as in example 1 was conducted.
Example 3
The lithium ion battery pole piece provided in this embodiment includes: a positive pole piece and a negative pole piece;
The positive pole piece comprises a first current collector, a lithium-free positive pole material layer and a first lithium supplementing material layer which are sequentially arranged; the negative electrode plate comprises a second current collector, a lithium-free negative electrode material layer and a second lithium supplementing material layer which are sequentially arranged;
The lithium supplementing surface capacity of the positive pole piece and the negative pole piece is 80% of the reversible surface capacity of the positive pole piece respectively; the reversible surface capacity of the negative pole piece is 1.10 times of the reversible surface capacity of the positive pole piece;
The thickness of the first lithium supplementing material layer is 20 mu m; the thickness of the second lithium supplementing material layer is 9 mu m; the lithium supplementing materials in the first lithium supplementing material layer and the second lithium supplementing material layer are metal lithium foils;
Otherwise, the same as in example 1 was conducted.
Example 4
The lithium ion battery pole piece provided in this embodiment includes: a positive pole piece and a negative pole piece;
The positive pole piece comprises a first current collector, a lithium-free positive pole material layer and a first lithium supplementing material layer which are sequentially arranged; the negative electrode plate comprises a second current collector, a lithium-free negative electrode material layer and a second lithium supplementing material layer which are sequentially arranged;
The capacity of the lithium supplementing surface of the positive electrode plate is 40% of the capacity of the reversible surface of the positive electrode plate, the capacity of the lithium supplementing surface of the negative electrode plate is 70% of the capacity of the reversible surface of the positive electrode plate, and the capacity of the reversible surface of the negative electrode plate is 1.10 times of the capacity of the reversible surface of the positive electrode plate;
The thickness of the first lithium supplementing material layer is 11 mu m; the thickness of the second lithium supplementing material layer is 19 mu m; the lithium supplementing materials in the first lithium supplementing material layer and the second lithium supplementing material layer are metal lithium foils;
the lithium-free positive electrode material layer comprises the following components in parts by mass: 80 parts of carbon fluoride, 18 parts of conductive agent and 2 parts of binder, wherein the positive electrode surface density is 8mg/cm 2;
The lithium-free anode material layer comprises the following components in parts by mass: 98 parts of artificial graphite, 2 parts of conductive agent and 0.5 part of binder, wherein the surface density of the negative electrode is 15mg/cm 2.
The preparation method of the lithium ion battery pole piece provided by the embodiment is the same as that of the embodiment 1.
Example 5
The lithium ion battery provided by the embodiment adopts the lithium ion battery pole piece of the embodiment 1, and the preparation method comprises the following steps:
1. selecting a 9-micron PE base film and a 2-micron boehmite coating as a diaphragm;
2. Assembling a lithium ion battery pole piece and a diaphragm into a 5Ah battery cell, and placing the battery cell in an oxygen atmosphere at 90 ℃ for baking for 24 hours;
3. electrolyte solution: liPF6 was dissolved in Ethylene Carbonate (EC): ethyl Methyl Carbonate (EMC) =3: 7, the concentration of LiPF6 in the solvent is 1mol/L; and (5) injecting liquid into the baked battery cell.
Example 6
The specific steps of the lithium ion battery provided in this embodiment, which adopts the lithium ion battery pole piece in embodiment 2, are basically the same as those in embodiment 5, except that the baking temperature is 40 ℃, and the baking time is 24 hours.
Example 7
The specific steps of the lithium ion battery provided in this embodiment, which adopts the lithium ion battery pole piece in embodiment 3, are basically the same as those in embodiment 5, except that the baking temperature is 100 ℃, and the baking time is 1h.
Example 8
The lithium ion battery provided in this embodiment adopts the lithium ion battery pole piece in embodiment 4, and the specific steps are the same as those in embodiment 5.
Example 9
The difference between the lithium ion battery pole piece provided by the embodiment and the embodiment 1 is that the reversible surface capacity of the negative pole piece is 1.02 times of the reversible surface capacity of the positive pole piece, and the preparation method of the lithium ion battery pole piece is the same as that of the embodiment 1;
The lithium ion battery provided by the embodiment adopts the lithium ion battery pole piece, and the preparation method of the lithium ion battery is the same as that of the embodiment 5.
Example 10
The difference between the lithium ion battery pole piece provided by the embodiment and the embodiment 1 is that the reversible surface capacity of the negative pole piece is 1.15 times of the reversible surface capacity of the positive pole piece, and the preparation method of the lithium ion battery pole piece is the same as that of the embodiment 1;
The lithium ion battery provided by the embodiment adopts the lithium ion battery pole piece, and the preparation method of the lithium ion battery is the same as that of the embodiment 5.
Comparative example 1
50 Μm thick metallic lithium was provided as a negative electrode on each side of a 4.5 μm thick copper foil, and the other was the same as in example 1. The preparation method of the lithium ion battery is the same as in example 5.
Comparative example 2
The lithium ion battery pole piece provided by the comparative example has the lithium supplementing surface capacity of the positive pole piece and the negative pole piece which are respectively 20% of the reversible surface capacity of the positive pole piece.
Otherwise, the same as in example 1 was conducted. The preparation method of the lithium ion battery is the same as in example 5.
Comparative example 3
The reversible surface capacity of the negative electrode plate of the lithium ion battery pole plate provided by the comparative example is 1.3 times of that of the positive electrode plate;
otherwise, the same as in example 1 was conducted. The preparation method of the lithium ion battery is the same as in example 5.
Experimental example
The lithium ion batteries prepared in examples 5 to 10 and comparative examples 1 to 3 were subjected to performance test as follows:
room temperature cycle life: 0.5C charge and discharge cycle until the capacity retention rate reaches 80% cycle times;
2C rate retention: 0.33C is fully charged, 2C and 0.33C are respectively discharged, and the discharge capacity of 2C is divided by the discharge capacity of 0.33C;
Volume deformation: full electrical thickness of 0.33C divided by initial cell thickness.
The results are shown in Table 1.
TABLE 1
From the aspect of performance, compared with the comparative example, the lithium ion battery prepared by the invention has better cycle life, high rate retention and low volume deformation rate, and has good electrochemical performance.
As can be seen from comparison of comparative example 1 and example 5, the cycle life and rate retention of the pure metallic lithium negative electrode are both significantly reduced, and the volume deformation is significantly increased.
As can be seen from comparison of comparative example 2 and example 5, when the lithium supplementing surface capacities of the positive electrode sheet and the negative electrode sheet are not within the range of 30% -80% of the reversible surface capacity of the positive electrode sheet, the cycle life and the rate retention rate are significantly reduced.
As can be seen from comparison of the comparative example 3 and the example 5, when the reversible surface capacity of the negative electrode sheet is not within 1.02-1.15 times of the reversible surface capacity of the positive electrode sheet, the cycle life and the rate-keeping rate are both obviously reduced, and the volume deformation is obviously increased.
While the invention has been illustrated and described with reference to specific embodiments, it is to be understood that the above embodiments are merely illustrative of the technical aspects of the invention and not restrictive thereof; those of ordinary skill in the art will appreciate that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present invention; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; it is therefore intended to cover in the appended claims all such alternatives and modifications as fall within the scope of the invention.
Claims (9)
1. A lithium ion battery pole piece, comprising: a positive pole piece and a negative pole piece;
the positive electrode plate comprises a first current collector, a lithium-free positive electrode material layer and a first lithium supplementing material layer which are sequentially arranged;
the negative electrode piece comprises a second current collector, a lithium-free negative electrode material layer and a second lithium supplementing material layer which are sequentially arranged;
The capacity of the lithium supplementing surfaces of the positive pole piece and the negative pole piece is 30% -80% of the capacity of the reversible surface of the positive pole piece respectively.
2. The lithium ion battery pole piece of claim 1, wherein the reversible surface capacity of the negative pole piece is 1.02-1.15 times the reversible surface capacity of the positive pole piece.
3. The lithium ion battery pole piece of claim 1, wherein the thickness of the first lithium supplementing material layer is 8-20 μm;
The thickness of the second lithium supplementing material layer is 8-20 mu m.
4. The lithium-ion battery pole piece of claim 1, wherein the lithium-compensating material in the first layer of lithium-compensating material comprises: a metal lithium;
the lithium supplementing material in the second lithium supplementing material layer comprises: and lithium metal.
5. The lithium ion battery pole piece according to claim 1, wherein the lithium-free positive electrode material layer comprises, in parts by mass: 80-97 parts of a lithium-free positive electrode active material, 0.5-18 parts of a conductive agent and 0.5-2 parts of a binder;
the lithium-free positive electrode active material includes: at least one of carbon fluoride, iron trifluoride, titanium disulfide, molybdenum disulfide, iron disulfide, manganese dioxide, elemental sulfur, or vulcanized polyacrylonitrile.
6. The lithium ion battery pole piece according to claim 1, wherein the lithium-free negative electrode material layer comprises, in parts by mass: 95-98 parts of lithium-free anode active material, 0.5-2 parts of conductive agent and 0.5-3 parts of binder;
the lithium-free anode active material includes: graphite, silicon alloy, tin alloy, silicon carbon, silicon oxygen, tin carbon, tin oxygen, soft carbon or hard carbon.
7. The method for preparing the lithium ion battery pole piece according to any one of claims 1 to 6, comprising the following steps:
Coating a lithium-free positive electrode material on a first current collector, and performing first drying and first rolling to obtain a positive electrode plate precursor; attaching the lithium supplementing material in the first lithium supplementing material layer on the positive electrode plate precursor to obtain a positive electrode plate;
coating a lithium-free anode material on a second current collector for second drying and second rolling to obtain an anode piece precursor; and attaching the lithium supplementing material in the second lithium supplementing material layer on the anode electrode plate precursor to obtain the anode electrode plate.
8. The lithium ion battery is characterized in that the lithium ion battery pole piece prepared by the preparation method of the lithium ion battery pole piece in claim 7 is assembled, dried, injected with liquid and formed.
9. The lithium ion battery of claim 8, wherein the temperature of the drying process is 40-100 ℃;
the drying treatment time is 1-24 h.
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