CN110611117A - Lithium ion battery and positive pole piece - Google Patents
Lithium ion battery and positive pole piece Download PDFInfo
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- CN110611117A CN110611117A CN201810620037.2A CN201810620037A CN110611117A CN 110611117 A CN110611117 A CN 110611117A CN 201810620037 A CN201810620037 A CN 201810620037A CN 110611117 A CN110611117 A CN 110611117A
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- ion battery
- lithium ion
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium ion battery and a positive pole piece, wherein the positive pole piece comprises a positive current collector and a positive diaphragm coated on the positive current collector, the positive diaphragm comprises a positive active substance, a binder and a conductive agent, the positive diaphragm also comprises an additive, and the additive comprises a mixture of one or more of polyethylene glycol, polyoxyethylene, polyoxypropylene and derivatives thereof and lithium salt. The additive contained in the positive membrane can be subjected to oxidative decomposition under a certain voltage, and the decomposition product can improve the first charge-discharge efficiency of the lithium ion battery and can improve the multiplying power and the cycle performance of the battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery manufacturing, and particularly relates to a lithium ion battery and a positive pole piece thereof.
Background
Petroleum and coal are the foundation of energy economy at present, but because the reserves of petroleum fuel and coal are limited and the pollution problem is increasingly prominent in the using process, the high-grade clean energy is urgently needed to be searched. Since sony corporation invented lithium ion batteries using carbon materials as negative electrodes, lithium ion batteries have attracted extensive attention from academia and business industries, have become one of the energy sources of the main portable electronic devices, and can be further applied to the power field of electric vehicles and the like. The lithium ion battery has great development with the advantages of high single voltage, large specific energy, small self-discharge, good cycle performance, no memory effect and the like, and the development of the lithium ion battery is a very effective way for relieving energy shortage and protecting the environment.
Because of the advantages, lithium ion batteries are becoming a new energy source preferred by various automobile manufacturers. However, due to some characteristics of the motion of the automobile, the automobile field puts higher requirements on the performance of the lithium ion battery, the lithium ion battery is required to meet the fast charge characteristic, and continuous heavy current discharge can be realized to meet the power requirement, and the requirements not only require that the lithium ion battery has high-rate charge and discharge performance, but also need to have high energy density.
At present, researchers all aim to solve the problems, on one hand, the rate charge and discharge performance of lithium ions is improved by improving the lithium ion diffusion capacity of positive and negative electrode materials, the ionic conductivity of an electrolyte and adding a conductive agent into an active substance; on the other hand, the ratio of positive and negative active materials is increased by using positive and negative electrode materials with high specific capacity, and the energy density of the battery is improved by using a pre-lithium intercalation technology. In addition, the rate capability and the energy density of the battery are respectively improved through the design of the lithium ion battery. However, in order to improve the rate performance of the lithium ion battery and increase the energy density of the battery, the improvement needs to be made from multiple aspects, the process is complex, and the improvement is limited. Therefore, a simple, convenient and effective method for simultaneously improving the rate capability and energy density of the battery is needed.
Disclosure of Invention
One of the objects of the present invention is: the positive pole piece can improve the first charge-discharge efficiency of the lithium ion battery and can improve the multiplying power and the cycle performance of the battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
the utility model provides a lithium ion battery positive pole piece, includes that the anodal mass flow body and coat the anodal diaphragm on the anodal mass flow body, anodal diaphragm includes anodal active material, binder and conductive agent, its characterized in that: the positive electrode membrane also comprises an additive, wherein the additive comprises a mixture of one or more of polyethylene glycol, polyethylene oxide, polypropylene oxide and derivatives thereof and lithium salt.
The additive comprises a mixture of one or two of polyethylene glycol or polyethylene oxide and lithium salt.
The molecular weight of the polyethylene glycol is selected within the range of 200-20000, and the molecular weight of the polyoxyethylene is selected within 105～107Within the range.
LiCF is selected as the lithium salt3SO3、Li(CF3SO3)2N、LiPF6、LiBF4、LiAsF6、LiClO4One or more of LiBOB or lidob (i.e., lithium difluorooxalato borate).
The mass of one or two of the polyethylene glycol or the polyoxyethylene accounts for 0.5-10% of the total mass of the positive electrode membrane, and is preferably 0.5-1.8%. The mass of the lithium salt is 0.1-5% of the total mass of the positive electrode diaphragm, and preferably 0.2-0.5%. According to the invention, when the content of the additive is limited to the above content, the first charge-discharge efficiency of the battery can be effectively improved, and the multiplying power and the cycle performance of the battery can be improved. Experiments show that the battery capacity is reduced and the performance is not obviously improved when the amount of the additive is too high.
Meanwhile, the positive active material of the positive pole piece of the lithium ion battery is selected from lithium manganate (LiMn)2O4) Lithium cobaltate (LiCoO)2) Lithium nickel cobalt manganese oxide (LiNi)xMnyCo1-(x+y)O2) Wherein x is less than 1, y is less than 1, and x + y is less than 1.
The conductive agent of the lithium ion battery positive pole piece is one or more of acetylene black, conductive carbon, carbon fiber, carbon nanotube, Ketjen black and graphene.
The invention also aims to provide a lithium ion battery, which comprises a positive pole piece, a negative pole piece, a diaphragm and electrolyte, wherein the diaphragm is arranged between the positive pole piece and the negative pole piece at an interval, and the positive pole piece is the positive pole piece of the lithium ion battery.
The invention has the beneficial effects that:
when the voltage of the lithium ion battery reaches a certain value during the first charging process (but the cut-off voltage is not reached to 4.2V), the anode active material as the transition metal oxide does not undergo oxidative decomposition in the voltage range, and the mixture of one or more of polyethylene glycol, polyethylene oxide, polypropylene oxide and derivatives thereof and lithium salt undergoes oxidative decomposition (about 3.9V) when the lithium ion battery is added with the additive; on one hand, the decomposition product is complexed with lithium ions and is diffused into the electrolyte, and further the decomposition product is transmitted inside the electrolyte, so that the conductivity of the electrolyte is improved, the number of current carriers is increased, the interface reaction frequency is improved, and the multiplying power charge and discharge performance of the battery is improved; on the other hand, the additive in the positive electrode membrane is oxidized and decomposed, so that lithium ions in the positive electrode membrane are preferentially inserted into the negative electrode, the lithium removal of the positive electrode material is reduced, the lithium ions can be extracted from the negative electrode and inserted into the positive electrode when the battery is discharged, and the first efficiency of the battery is improved. In addition, the lithium ion battery prepared by the positive pole piece also has good cycle performance.
Drawings
Fig. 1 is a comparison of first charge and discharge curves of batteries of comparative example and example in the present invention.
FIG. 2 is a comparison of the rate discharge performance of the batteries of comparative example and example in the present invention.
Fig. 3 is a comparison of the cycle performance at 25 c of the batteries of the comparative example and example of the present invention at normal temperature.
Detailed Description
The present invention will be further described by comparing specific examples with comparative examples. The scope of the invention is not limited to these examples.
Example 1
Preparing a positive pole piece: the positive active material of nickel cobalt lithium manganate (LiNi)0.6Co0.2Mn0.2O2) Conductive carbon (Super-P) as conductive agent, polyvinylidene fluoride (PVDF) as adhesive, and polyethylene oxide (PEO) with molecular weight of 1000000]Lithium salt Li (CF)3SO3)2N is according to 94: 2: 2: 1.8: 0.2 was mixed in a solvent of N-methylpyrrolidone (NMP) by mass ratio, and stirred uniformly to prepare a positive electrode mixture slurry. And coating the obtained positive electrode slurry on an aluminum foil, drying, rolling and shearing to form a positive electrode plate.
Preparing a negative pole piece: mixing a negative active material artificial graphite, a conductive agent conductive carbon (Super-P), a binder Styrene Butadiene Rubber (SBR) and a thickener sodium carboxymethyl cellulose (CMC) according to a ratio of 94: 2: 2: 2 in the solvent water, and stirring uniformly to obtain the cathode mixture slurry. And coating the obtained negative electrode slurry on a copper foil, drying, rolling and shearing to form a negative electrode pole piece.
Preparing an electrolyte: uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and Ethyl Methyl Carbonate (EMC) in a volume ratio of 1:1:1, adding a certain amount of lithium hexafluorophosphate to prepare 1mol/L electrolyte, adding a film forming additive, namely Vinylene Carbonate (VC), which accounts for 1 wt% of the total weight of the electrolyte, into the electrolyte, and uniformly mixing to obtain the electrolyte.
Preparing a lithium ion battery: and (3) sequentially laminating the prepared positive pole piece and the diaphragm-coated negative pole piece according to the negative pole, the positive pole and the negative pole to prepare a battery core, welding a positive pole lug and a negative pole lug, packaging the battery core by using an aluminum plastic film, leaving a liquid injection port, and injecting electrolyte into the battery to prepare the lithium ion battery.
Example 2
The positive active material of nickel cobalt lithium manganate (LiNi)0.6Co0.2Mn0.2O2) Conductive carbon (Super-P) as conductive agent, polyvinylidene fluoride (PVDF) as adhesive and polyethylene glycol [ (PEG) with molecular weight of 10000]Polyethylene oxide [ (PEO) molecular weight 5000000]Lithium salt LiCF3SO3According to a 94: 2: 2: 0.6: 1.2: 0.2 was mixed in a solvent of N-methylpyrrolidone (NMP) by mass ratio, and stirred uniformly to prepare a positive electrode mixture slurry. And coating the obtained positive electrode slurry on an aluminum foil, drying, rolling and shearing to form a positive electrode plate.
A lithium ion battery was prepared according to the same method as in example 1 using the positive electrode sheet prepared in this example.
Example 3
The positive active material of nickel cobalt lithium manganate (LiNi)0.6Co0.2Mn0.2O2) Conductive carbon (Super-P) as conductive agent, polyvinylidene fluoride (PVDF) as adhesive and methoxy polyethylene glycol [ (mPEG) with molecular weight of 10000]Polyethylene oxide [ (PEO) molecular weight 5000000]Lithium salt LiDOFB 94: 2: 1.5: 0.5: 1.5: 0.5 mass ratio was mixed in a solvent of N-methylpyrrolidone (NMP), and stirred uniformly, thereby preparing a positive electrode mixture slurry. And coating the obtained positive electrode slurry on an aluminum foil, drying, rolling and shearing to form a positive electrode plate.
A lithium ion battery was prepared according to the same method as in example 1 using the positive electrode sheet prepared in this example.
Example 4
The positive active material of nickel cobalt lithium manganate (LiNi)0.6Co0.2Mn0.2O2) Conductive carbon (Super-P) as conductive agent, polyvinylidene fluoride (PVDF) as adhesive, and polyethylene oxide (PEO) with molecular weight of 2000000]Lithium salt LiCF3SO3、Li(CF3SO3)2N is according to 94: 2: 2: 1.6: 0.2: 0.2 was mixed in a solvent of N-methylpyrrolidone (NMP) by mass ratio, and stirred uniformly to prepare a positive electrode mixture slurry. The obtained positive electrode slurry was coated on an aluminum foil and driedAnd (4) rolling and shearing after drying to form the positive pole piece.
A lithium ion battery was prepared according to the same method as in example 1 using the positive electrode sheet prepared in this example.
Example 5
The positive active material of nickel cobalt lithium manganate (LiNi)0.6Co0.2Mn0.2O2) Conductive carbon (Super-P) as a conductive agent, polyvinylidene fluoride (PVDF) as a binder, and polypropylene oxide [ (PPO) with a molecular weight of 1000000]Lithium salt Li (CF)3SO3)2N is according to 94: 2: 2: 1.8: 0.2 was mixed in a solvent of N-methylpyrrolidone (NMP) by mass ratio, and stirred uniformly to prepare a positive electrode mixture slurry. And coating the obtained positive electrode slurry on an aluminum foil, drying, rolling and shearing to form a positive electrode plate.
A lithium ion battery was prepared according to the same method as in example 1 using the positive electrode sheet prepared in this example.
Comparative example 1
The positive active material of nickel cobalt lithium manganate (LiNi)0.6Co0.2Mn0.2O2) Conductive carbon (Super-P) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder were as follows 94: 3: 3 in the solvent of N-methyl pyrrolidone (NMP), and uniformly stirring to prepare the positive electrode mixture slurry. And coating the obtained positive electrode slurry on an aluminum foil, drying, rolling and shearing to form a positive electrode plate.
A lithium ion battery was prepared according to the same method as in example 1 using the positive electrode sheet prepared in the comparative example.
Comparative example 2
The positive active material of nickel cobalt lithium manganate (LiNi)0.6Co0.2Mn0.2O2) Conductive carbon (Super-P) as conductive agent, polyvinylidene fluoride (PVDF) as adhesive, and polyethylene oxide (PEO) with molecular weight of 1000000]According to a 94: 2: 2: 2 in the solvent of N-methylpyrrolidone (NMP), and stirring uniformly to prepare a positive electrode mixture slurry. And coating the obtained positive electrode slurry on an aluminum foil, drying, rolling and shearing to form a positive electrode plate.
A lithium ion battery was prepared according to the same method as in example 1 using the positive electrode sheet prepared in the comparative example.
Electrochemical performance tests were performed on the lithium ion batteries of examples 1 to 5 and comparative examples 1 to 2:
testing the charge and discharge performance for the first time: and after the lithium ion battery is prepared, performing a charge-discharge pre-charge test by using current with 0.1C multiplying power.
And (3) rate discharge performance test: after the pre-charging of the lithium ion battery is finished, the lithium ion battery is charged to a full state at a constant temperature of 25 ℃ by current of 1C multiplying power, and then a discharge test is carried out by current of 10C multiplying power.
And (3) testing the cycle performance: after the pre-charging of the lithium ion battery is finished, the charging and discharging test is carried out at the constant temperature of 25 ℃ by using the current with the multiplying power of 1C.
The results of the electrochemical performance tests are summarized in table 1 below.
TABLE 1
The first charge-discharge curve of the batteries of the examples and the comparative examples is shown in the attached figure 1, and the first charge-discharge efficiency of the batteries of the examples 1 to 5 is obviously improved compared with that of the comparative examples from the data of the attached figure 1 and the data of the table 1. The first charge and discharge efficiency of the example 4 in the preferred embodiment is improved by 9.56% compared with the comparative example 1 and is improved by 9.38% compared with the comparative example 2.
FIG. 2 is a comparison of the rate discharge performance of the batteries of the examples and comparative examples. As can be seen by combining the data in table 1, the percent rate discharge capacities of the cells of examples 1-5 are all higher than the comparative cells. In the preferred embodiment, the percentage of the rate discharge capacity of example 4 is 31.03% higher than that of comparative example 1 and 26.99% higher than that of comparative example 2.
FIG. 3 is a graph showing the cycle performance at 25 ℃ at room temperature for the batteries of examples and comparative examples. As can be seen by combining fig. 3 and the data in table 1, the capacity retention rate of the batteries of examples 1-5 after 300 cycles is higher than that of the comparative batteries. The cycle efficiency of example 2 of the preferred embodiment was improved by 7.49% compared to comparative example 1 and by 6.61% compared to comparative example 2.
The results show that the positive pole piece prepared by the invention and the lithium ion battery prepared by the positive pole piece can not only improve the first charge-discharge efficiency of the lithium ion battery, but also improve the multiplying power and the cycle performance of the battery.
The above description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and it will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the principle of the present invention, and these modifications and improvements should be construed as the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. The utility model provides a lithium ion battery positive pole piece, includes that the anodal mass flow body and coat the anodal diaphragm on the anodal mass flow body, anodal diaphragm includes anodal active material, binder and conductive agent, its characterized in that: the positive electrode membrane also comprises an additive, wherein the additive comprises a mixture of one or more of polyethylene glycol, polyethylene oxide, polypropylene oxide and derivatives thereof and lithium salt.
2. The positive electrode plate of the lithium ion battery according to claim 1, wherein: the additive comprises a mixture of one or two of polyethylene glycol or polyethylene oxide and lithium salt.
3. The positive electrode plate of the lithium ion battery according to claim 1, wherein: the molecular weight of the polyethylene glycol is selected within the range of 200-20000, and the molecular weight of the polyoxyethylene is selected within 105～107Within the range.
4. The positive electrode plate of the lithium ion battery according to claim 1, wherein: LiCF is selected as the lithium salt3SO3、Li(CF3SO3)2N、LiPF6、LiBF4、LiAsF6、LiClO4One or more of LiBOB or lithium difluorooxalato borate, lidob.
5. The positive electrode plate of the lithium ion battery according to claim 1, wherein: the mass of one or two of the polyethylene glycol or the polyoxyethylene accounts for 0.5-10% of the total mass of the positive electrode membrane, and is preferably 0.5-1.8%.
6. The positive electrode plate of the lithium ion battery according to claim 1, wherein: the mass of the lithium salt is 0.1-5% of the total mass of the positive electrode diaphragm, and preferably 0.2-0.5%.
7. The positive electrode plate of the lithium ion battery according to claim 1, wherein: the positive active material is lithium manganate LiMn2O4Lithium cobaltate LiCoO2Lithium nickel cobalt manganese LiNixMnyCo1-(x+y)O2Wherein x is less than 1, y is less than 1, and x + y is less than 1.
8. The positive electrode plate of the lithium ion battery according to claim 1, wherein: the conductive agent is one or more of acetylene black, conductive carbon, carbon fiber, carbon nanotube, ketjen black and graphene.
9. The utility model provides a lithium ion battery, includes positive pole piece, negative pole piece, interval in diaphragm between positive pole piece and the negative pole piece to and electrolyte, its characterized in that: the positive pole piece is the positive pole piece of the lithium ion battery of any one of claims 1 to 8.
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| CN201810620037.2A CN110611117A (en) | 2018-06-15 | 2018-06-15 | Lithium ion battery and positive pole piece |
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| CN201810620037.2A CN110611117A (en) | 2018-06-15 | 2018-06-15 | Lithium ion battery and positive pole piece |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111793824A (en) * | 2020-07-21 | 2020-10-20 | 苏州华赢新能源材料科技有限公司 | Surface-modified high-nickel cathode material and preparation method and application thereof |
| CN115832207A (en) * | 2022-01-05 | 2023-03-21 | 宁德时代新能源科技股份有限公司 | Pole piece slurry, pole piece, preparation method of pole piece, lithium ion secondary battery, battery module, battery pack and electric device |
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| CN103022484A (en) * | 2012-12-15 | 2013-04-03 | 华中科技大学 | Lithium iron conductive complex modified lithium iron phosphate anode material and preparation method thereof |
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- 2018-06-15 CN CN201810620037.2A patent/CN110611117A/en active Pending
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| CN103022484A (en) * | 2012-12-15 | 2013-04-03 | 华中科技大学 | Lithium iron conductive complex modified lithium iron phosphate anode material and preparation method thereof |
Non-Patent Citations (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111793824A (en) * | 2020-07-21 | 2020-10-20 | 苏州华赢新能源材料科技有限公司 | Surface-modified high-nickel cathode material and preparation method and application thereof |
| CN111793824B (en) * | 2020-07-21 | 2022-05-24 | 苏州华赢新能源材料科技有限公司 | Surface-modified high-nickel cathode material and preparation method and application thereof |
| CN115832207A (en) * | 2022-01-05 | 2023-03-21 | 宁德时代新能源科技股份有限公司 | Pole piece slurry, pole piece, preparation method of pole piece, lithium ion secondary battery, battery module, battery pack and electric device |
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Application publication date: 20191224 |