WO2021184220A1 - Lithium ion start-stop power supply capable of being pre-lithiated and preparation method therefor - Google Patents

Lithium ion start-stop power supply capable of being pre-lithiated and preparation method therefor Download PDF

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WO2021184220A1
WO2021184220A1 PCT/CN2020/079786 CN2020079786W WO2021184220A1 WO 2021184220 A1 WO2021184220 A1 WO 2021184220A1 CN 2020079786 W CN2020079786 W CN 2020079786W WO 2021184220 A1 WO2021184220 A1 WO 2021184220A1
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lini
feo
power supply
stop power
electrode
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Chinese (zh)
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陈忠伟
余爱萍
毛治宇
熊俊威
黄明
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温州玖源锂电池科技发展有限公司
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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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  • the invention belongs to the technical field of lithium ion start-stop power supplies, and specifically relates to a lithium ion start-stop power supply capable of prelithiation and a preparation method thereof.
  • the automobile lithium-ion start-stop system saves fuel by more than 8% in urban road conditions, and can reduce CO 2 emissions, and can start the car quickly and safely. Therefore, the lithium-ion start-stop power supply has become a main engine factory.
  • Lithium-ion start-stop power supplies have high technical requirements in terms of power density, rate performance, etc., and need to overcome difficulties such as high current discharge at low temperatures, operation stability at high temperatures, and storage stability. Higher technical thresholds require battery companies. Start with the key battery materials to improve the overall performance of the lithium-ion start-stop power supply. Hard carbon is a commonly used electrode material in lithium-ion batteries, and has considerable market prospects. It has a large rate of charge and discharge energy, even at low temperatures, it can also show its rapid lithium insertion ability. However, what restricts its development is that as the negative electrode of the power supply, it has a very low first charge and discharge efficiency, only about 80%.
  • Li 5 FeO 4 is a recently reported ideal lithium source material. In theory, each mole of Li 5 FeO 4 can provide 5 lithium ions, and its specific capacity contribution can reach 867 mAh/g. As a positive electrode lithium source, it can release a large amount of lithium ions during the first charge, which significantly improves the first efficiency of the power supply.
  • the electrode reaction is as follows:
  • nickel-cobalt-manganese ternary materials are the most common. This material combines the synergistic effect of Ni-Co-Mn and combines good cycle performance of LiCoO 2 , high specific capacity of LiNiO 2 and low cost and safety of LiMnO 2
  • advantages of good performance are currently the mainstream of lithium-ion battery cathode materials, which have advantages in battery specific energy, specific power, high-rate charging, and low-temperature performance.
  • Pre-lithiation means that for a full battery, the SEI film formed at the negative electrode interface will consume the lithium ions extracted from the positive electrode and reduce the battery capacity. If a lithium source can be found outside the cathode material, the formation of the SEI film will consume the lithium ions of the external lithium source, so that the lithium ions deintercalated from the cathode will not be wasted in the formation process, and the full battery capacity can be increased. . This process of providing an external lithium source is pre-lithiation.
  • the main content is that he invented a porous carbon/Li 5 FeO 4 composite material as a positive electrode material.
  • the main difference from the present invention is 1.
  • the field of the present invention is the field of lithium ion start-stop power supplies; 2.
  • the composite material in the present invention is LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material.
  • US patent US 8313721 B2 "Lithium-oxygen (AIR) electrochemical cells and batteries” describes a lithium-air battery, which involves Li 5 FeO 4 material, but it belongs to a different technical field from the present invention, and its content is also It is not related to the present invention.
  • the cathode material involved is LiFePO 4
  • the Li 5 FeO 4 material is used as Battery additives.
  • the prior art there is currently no disclosure of using ternary nickel-cobalt-manganese materials and Li 5 FeO 4 materials to make LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite materials, and applying the composite materials to Kai In the field of power-off technology, related technologies to obtain power-off power with excellent performance.
  • the electrode material is LiNi made by compounding a ternary nickel-cobalt-manganese material with a Li 5 FeO 4 material. x Co y Mn z O 2 /Li 5 FeO 4 composite material. This composite material is used as the positive electrode of the electrode group and the hard carbon negative electrode to prepare a lithium ion start-stop power supply. Its electrochemical performance is better than that of the current commercial lithium-ion start-stop power supply. obvious advantage.
  • the purpose of the present invention is to solve the shortcomings of the existing lithium ion start-stop power supply such as specific energy, specific power, low charge and discharge times, poor low-temperature performance, etc., so as to provide a pre-lithiated lithium-ion start-stop power supply and the same
  • the preparation method, the lithium ion start-stop power supply prepared according to the method of the present invention has high power, high first-time efficiency and good low temperature characteristics.
  • a pre-lithiated lithium ion start-stop power supply wherein the Li 5 FeO 4 is made by mixing Li 2 O and Fe 2 O 3 at a molar ratio of 5:1. The amount is mechanically mixed, pressed into tablets, and finally sintered at high temperature to produce.
  • a lithium ion start-stop power supply capable of pre-lithiation, wherein the LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material is obtained by combining LiNi x Co y Mn z O 2 and Li 5 FeO 4 are mixed in a mass ratio of (0.8 ⁇ 0.98):(0.02 ⁇ 0.2) and then ball milled.
  • a lithium ion start-stop power supply capable of prelithiation wherein the LiNi x Co y Mn z O 2 is selected from LiNi 1/3 Co 1/3 Mn 1/3 O 2.
  • LiNi 0.5 Co 0.2 Mn 0.3 O 2 LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 .
  • Another embodiment of the present invention also provides a method for preparing the above-mentioned prelithiated lithium ion start-stop power supply, wherein the method includes the following steps:
  • a method for preparing a pre-lithiated start-stop power supply wherein, in the step (1), the LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite
  • the material is prepared by the following steps:
  • Li 2 O and Fe 2 O 3 After mixing Li 2 O and Fe 2 O 3, they are pressed into tablets and sintered at 700-900° C. for 15-25 hours to obtain Li 5 FeO 4 materials.
  • Li 5 FeO 4 and LiNi x Co y Mn z O 2 are mixed and ball milled, and then sieved to obtain a LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material.
  • a method for preparing a pre-lithiated start-stop power supply wherein, in the step a, the molar ratio of Li 2 O and Fe 2 O 3 is 5:1.
  • the mass ratio of the LiNi x Co y Mn z O 2 and Li 5 FeO 4 It is (0.8 ⁇ 0.98):(0.02 ⁇ 0.2).
  • the LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material is By mixing Li 5 FeO 4 and LiNi x Co y Mn z O 2 into a ball milling tank lined with zirconia material, using high-purity zirconia balls as the ball milling medium, the weight ratio of the balls is 60:1. It is obtained by sieving after ball milling for 2-24h under the condition of rotating speed of 300-600rmp/min.
  • a method for preparing a pre-lithiated start-stop power supply wherein, in the step (2), the LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite
  • the mass ratio of material, binder, and conductive agent is (80 ⁇ 98):(1 ⁇ 5):(0.5 ⁇ 10).
  • the binder is PVDF with a mass fraction of 2%-10% Solution
  • the solvent is an NMP solution, which is added at a solid content of 40% to 70%.
  • a method for preparing a pre-lithiated start-stop power supply wherein, in the step (3), the mass ratio of the graphite or hard carbon, the binder, and the conductive agent is It is (80 ⁇ 98):(1 ⁇ 5):(0.5 ⁇ 8).
  • a method for preparing a pre-lithiated start-stop power supply wherein, in the step (3), the binder is an acrylonitrile multi-element copolymer, a methylol fiber One or more of vegetable and styrene-butadiene rubber; the solvent is water, which is added at a solid content of 40% to 70%.
  • the conductive agent is selected from one or more of carbon black, conductive graphite, carbon fiber, and carbon nanotube .
  • the LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material can simultaneously combine with LiNi x Co y Mn z O 2 and has excellent battery specific energy, specific power, high rate charging, low temperature performance and Li 5 FeO 4 It has the advantages of high specific capacity and significant first-time efficiency.
  • the prepared lithium-ion start-stop power supply has high power, high first-time efficiency and good low-temperature characteristics after assembly and testing, and its first-time efficiency can reach 90% to 92%.
  • the power supply can achieve continuous discharge at a super-high rate, such as 40C, and the discharge capacity can reach 79.5% of the initial capacity; by testing the low-temperature performance of the soft-packed cell, it can achieve high-rate discharge at -20°C , Such as 20C rate discharge, the capacity can reach 51.6% of the initial capacity.
  • the preparation method of the start-stop power supply provided by the present invention has a simple process, and the whole process is similar to the current battery industrial production process, and has the advantages of low cost and easy realization of industrialization.
  • Fig. 1 is a room temperature rate performance test diagram of a prelithiated lithium ion start-stop power supply prepared in Example 1 of the present invention
  • Fig. 2 is a capacity-current performance curve at room temperature of a prelithiated lithium ion start-stop power supply prepared in Example 1 of the present invention
  • Fig. 3 is a low-temperature performance test diagram of a lithium ion start-stop power supply capable of pre-lithiation prepared in Example 1 according to the present invention at -20°C.
  • Li 2 O and Fe 2 O 3 were mechanically mixed at a molar ratio of 5:1 and then pressed into tablets, and sintered at 850° C. for 20 hours to obtain Li 5 FeO 4 materials.
  • the LiNi 0.6 Co 0.2 Mn 0.2 O 2 purchased from Beijing Dangsheng Material Technology Co., Ltd., China
  • LiNi 0.6 Co 0.2 Mn 0.2 O 2 /Li 5 FeO 4 composite material, PVDF and carbon black were mixed uniformly at a mass ratio of 92:5:3, and then NMP solvent was added at a solid content of 50% and stirred for 3.5 hours.
  • the slurry is uniformly coated on double-sided aluminum foil to form a composite electrode.
  • the composite electrode material is dried and then rolled into a sheet and then cut into a positive electrode sheet (5.9cm ⁇ 10.9cm) with tabs (5.9cm ⁇ 10.9cm).
  • the positive and negative electrode sheets prepared above, using the PP/PE composite microporous membrane as the separator, are laminated in parallel according to 10 positive sheets and 11 negative sheets to complete the tab welding to obtain an electrode group.
  • Fig. 1 is a room temperature magnification performance test of a lithium-ion start-stop power supply prepared in Example 1 of the present invention
  • Fig. 2 is a room temperature capacity-current performance curve of a lithium-ion start-stop power supply prepared in Example 1 of the present invention.
  • the first efficiency of the lithium ion start-stop power supply prepared is 90% to 92%.
  • the rate performance is tested.
  • the power supply can also achieve continuous discharge and discharge at a super-large rate, such as 40C.
  • the capacity can reach 79.5% of the initial capacity.
  • Fig. 3 is a low-temperature performance test diagram of the lithium ion start-stop power supply prepared in Example 1 according to the present invention at -20°C.
  • Li 2 O and Fe 2 O 3 were mechanically mixed at a molar ratio of 5:1 and then pressed into tablets, and sintered at 900° C. for 25 hours to obtain Li 5 FeO 4 materials.
  • LiNi 0.5 Co 0.2 Mn 0.3 O 2 purchased from Beijing Dangsheng Material Technology Co., Ltd., China
  • Li 5 FeO 4 9.8:0.2
  • zirconia balls mixed with zirconia balls according to the ball weight ratio of 60:1 and put them into a ball milling tank lined with zirconia material at a speed of 600rmp/min Dry ball milling for 13 hours, then sieving to obtain LiNi 0.5 Co 0.2 Mn 0.3 O 2 /Li 5 FeO 4 composite material.
  • LiNi 0.5 Co 0.2 Mn 0.3 O 2 /Li 5 FeO 4 composite material, PVDF and carbon black were mixed uniformly at a mass ratio of 85:5:10, and then NMP solvent was added at a solid content of 70% and stirred for 5 hours.
  • the resulting slurry The material is uniformly coated on double-sided aluminum foil to form a composite electrode.
  • the composite electrode material is dried and then rolled into a sheet, and then cut into a positive electrode sheet (5.9cm ⁇ 10.9cm) with tabs (5.9cm ⁇ 10.9cm).
  • the positive and negative electrode sheets prepared above, using the PP/PE composite microporous membrane as the separator, are laminated in parallel according to 10 positive sheets and 11 negative sheets to complete the tab welding to obtain an electrode group.
  • the prepared lithium-ion start-stop power supply has an initial efficiency of 85% to 87%.
  • the rate performance is tested.
  • the power supply can also achieve continuous discharge at a super-large rate, such as a 40C rate, and the discharge capacity can reach 75.3% of the initial capacity;
  • a super-large rate such as a 40C rate
  • the discharge capacity can reach 75.3% of the initial capacity;
  • the capacity can reach 49.6% of the initial capacity; the 500cy cycle performance measurement can reach 95.7%.
  • Li 2 O and Fe 2 O 3 were mechanically mixed at a molar ratio of 5:1 and then pressed into tablets, and sintered at 700° C. for 15 hours to obtain Li 5 FeO 4 materials.
  • the LiNi 1/3 Co 1/3 Mn 1/3 O 2 purchased from Beijing Dangsheng Material Technology Co., Ltd., China
  • LiNi 1/3 Co 1/3 Mn 1/3 O 2 /Li 5 FeO 4 composite material, PVDF, carbon black and conductive graphite are mixed uniformly at a mass ratio of 98:1:1, and then the solid content is 40%. Add NMP solvent and stir for 2 hours. The resulting slurry is evenly coated on double-sided aluminum foil to form a composite electrode. The composite electrode material is dried and then rolled into a sheet and then cut into a positive electrode sheet with tabs ( 5.9cm ⁇ 10.9cm) several finished products.
  • the graphite material, hydroxymethyl cellulose, styrene-butadiene rubber, and carbon black are mixed uniformly in a mass ratio of 91:1:8, and then deionized water is added at a solid content of 70% and stirred for 2 hours.
  • the resulting slurry is evenly coated on the double
  • the carbon electrode is prepared by forming on the copper foil. The carbon electrode is dried and then rolled into a sheet, and then cut into a negative sheet (6.0cm ⁇ 11.0cm) with tabs (6.0cm ⁇ 11.0cm).
  • the positive and negative electrode sheets prepared above, using the PP/PE composite microporous film as the separator, are laminated in parallel according to 10 positive sheets and 11 negative sheets to complete the tab welding to obtain an electrode group.
  • the prepared lithium ion start-stop power supply has an initial efficiency of 90% to 92%.
  • the rate performance is tested.
  • the power supply can also achieve continuous discharge at a super-large rate, such as a 40C rate, and the discharge capacity can reach 82.8% of the initial capacity;
  • a super-large rate such as a 40C rate
  • the discharge capacity can reach 82.8% of the initial capacity;
  • the capacity can reach 54.1% of the initial capacity; its 500cy cycle performance can reach 97.1%.
  • Li 2 O and Fe 2 O 3 were mechanically mixed at a molar ratio of 5:1 and then pressed into tablets, and sintered at 850° C. for 20 hours to obtain Li 5 FeO 4 materials.
  • LiNi 0.8 Co 0.1 Mn 0.1 O 2 purchased from Beijing Dangsheng Material Technology Co., Ltd., China
  • Li 5 FeO 4 8:2
  • mixed with zirconia balls according to the ball weight ratio of 60:1 put them into a ball milling tank lined with zirconia material, at a speed of 500rmp/min Dry ball milling for 24 hours, then sieving to obtain LiNi 0.8 Co 0.1 Mn 0.1 O 2 Li 5 FeO 4 composite material.
  • LiNi 0.8 Co 0.1 Mn 0.1 O 2 /Li 5 FeO 4 composite material, PVDF and carbon black were mixed uniformly at a mass ratio of 92.5:2.5:5, and then NMP solvent was added at a solid content of 50% and stirred for 3.5 hours.
  • the slurry is uniformly coated on double-sided aluminum foil to form a composite electrode.
  • the composite electrode material is dried and then rolled into a sheet and then cut into a positive electrode sheet (5.9cm ⁇ 10.9cm) with tabs (5.9cm ⁇ 10.9cm).
  • the hard carbon material, hydroxymethyl cellulose, styrene butadiene rubber, and carbon black are mixed uniformly in a mass ratio of 93.5:2.5:4, and then deionized water is added at a solid content of 50% and stirred for 3.5 hours.
  • the resulting slurry is evenly coated Forming on double-sided copper foil to prepare a carbon electrode.
  • the carbon electrode is dried and then rolled into a sheet, and then cut into a negative electrode sheet (6.0cm ⁇ 11.0cm) with tabs (6.0cm ⁇ 11.0cm).
  • the positive and negative electrode sheets prepared above, using the PP/PE composite microporous membrane as the separator, are laminated in parallel according to 10 positive sheets and 11 negative sheets to complete the tab welding to obtain an electrode group.
  • the prepared lithium ion start-stop power supply has an initial efficiency of 93% to 94%.
  • the rate performance is tested.
  • the power supply can also achieve continuous discharge at a super-large rate, such as a 40C rate, and the discharge capacity can reach 72.9% of the initial capacity;
  • a super-large rate such as a 40C rate
  • the discharge capacity can reach 72.9% of the initial capacity;
  • By testing the low-temperature performance of the lithium-ion start-stop power supply it can achieve high-rate discharge at -20°C. For example, under 20C rate discharge, the capacity can reach 48.6% of the initial capacity; its 500cy cycle performance can reach 90.1%.
  • Example 1 uses LiNi 0.6 Co 0.2 Mn 0.2 O 2 /Li 5 FeO 4 composite material to prepare the positive electrode sheet, while Comparative Example 1 uses the method in Example 1.
  • the LiNi 0.6 Co 0.2 Mn 0.2 O 2 preparation method of LiNi 0.6 Co 0.2 Mn 0.2 O 2 is used to prepare a positive electrode sheet.
  • the other steps and conditions are the same, and the details are not repeated here.
  • the discharge capacity of the power supply can reach 65.2 of the initial capacity at a super-large rate, such as a 40C rate. %; By testing the low temperature performance of the lithium ion start-stop power supply, its capacity can reach 42.5% of the initial capacity at -20°C, such as at 20C rate discharge; its 500cy cycle performance can reach 89.5%.
  • Example 2 uses LiNi 0.5 Co 0.2 Mn 0.3 O 2 /Li 5 FeO 4 composite material to prepare the positive electrode sheet, while Comparative Example 2 uses the method in Example 2.
  • the LiNi 0.5 Co 0.2 Mn 0.3 O 2 preparation method of LiNi 0.5 Co 0.2 Mn 0.3 O 2 is used to prepare a positive electrode sheet.
  • the other steps and conditions are the same, and the details are not repeated here.
  • the discharge capacity of the power supply can reach the initial capacity at a super-large rate, such as a 40C rate.
  • By testing the low temperature performance of the lithium-ion start-stop power supply its capacity can reach 41.7% of the initial capacity at -20°C, such as at 20C rate discharge; its 500cy cycle performance measurement can reach 88.7% .
  • Comparative Example 3 uses LiNi 1/3 Co 1/3 Mn 1/3 O 2 /Li 5 FeO 4 composite material to make the positive electrode sheet, while Comparative Example 3 uses that LiNi 1/3 Co 1/3 Mn 1/3 O 2 positive electrode sheet prepared in Example 3 LiNi 1/3 Co 1/3 Mn 1/3 O 2 preparation obtained, the other steps and conditions are the same , I won’t go into details here.
  • the discharge capacity of the power supply can reach the initial capacity at a super-large rate, such as a 40C rate.
  • By testing the low-temperature performance of the lithium-ion start-stop power supply its capacity can reach 44.3% of the initial capacity at -20°C, such as at 20C rate discharge; its 500cy cycle performance measurement can reach 89.5% .
  • Example 4 uses LiNi 0.8 Co 0.1 Mn 0.1 O 2 /Li 5 FeO 4 composite material to prepare the positive electrode sheet, while Comparative Example 4 uses the method in Example 4.
  • the LiNi 0.8 Co 0.1 Mn 0.1 O 2 preparation method of LiNi 0.8 Co 0.1 Mn 0.1 O 2 is used to prepare a positive electrode sheet.
  • the other steps and conditions are the same, and the details are not repeated here.
  • the lithium ion start-stop power supply performance test data obtained in the above examples are compared through the table display, see Table 1 for details.
  • the pre-lithiated lithium ion start-stop power supply obtained according to the method of the present invention does not matter
  • the performance of the lithium-ion start-stop power supply in the comparative example is superior in terms of first efficiency, power, and low-temperature performance. Therefore, the lithium-ion start-stop power supply of the present invention has a wide range of application prospects.

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Abstract

Provided is a lithium ion start-stop power supply capable of being pre-lithiated, comprising a positive electrode and a negative electrode, wherein the positive electrode is mainly made of a LiNixCoyMnzO2/Li5FeO4 composite material, which satisfies x + y + z = 1. Also provided is a method for preparing the lithium ion start-stop power supply capable of being pre-lithiated. The method comprises the steps of preparing the LiNixCoyMnzO2/Li5FeO4 composite material, preparing the positive electrode and the negative electrode of the power supply, assembling the positive electrode and the negative electrode into the lithium ion start-stop power supply, etc. The start-stop power supply obtained according to the provided preparation method has a good specific energy, a good specific power, good charge and discharge times and a good low temperature performance, and is suitable for industrial production.

Description

一种可预锂化的锂离子启停电源及其制备方法Lithium ion start-stop power supply capable of pre-lithiation and preparation method thereof 技术领域Technical field
本发明属于锂离子启停电源技术领域，具体地，涉及一种可预锂化的锂离子启停电源及其制备方法。The invention belongs to the technical field of lithium ion start-stop power supplies, and specifically relates to a lithium ion start-stop power supply capable of prelithiation and a preparation method thereof.
背景技术Background technique
日前，欧盟委员会宣布，计划2021～2030年使欧盟新车二氧化碳排放量减少30％。欧盟当前的新车排放法规将于2021年到期，按照该法规，欧盟新车二氧化碳排放量须降至每公里95克；美国到2025年二氧化碳排放量须降至每公里97克；日本到2020年须降至122克。我国《节能与新能源汽车产业发展规划(2012-2020)》明确，2020年，传统燃油乘用车平均燃油消耗降至5.0L/100km，节能型乘用车新车平均燃料消耗量降至4.5L/100km以下。高工产研锂电研究所调研显示，汽车锂离子启停系统在城市路况中节省燃油达8％以上，而且能降低CO 2排放，可快速安全起动汽车，因此装载锂离子启停电源成为主机厂降低油耗的有效手段之一。 A few days ago, the European Commission announced that it plans to reduce carbon dioxide emissions from new cars in the EU by 30% from 2021 to 2030. The EU’s current new car emission regulations will expire in 2021. According to this regulation, the carbon dioxide emissions of new cars in the EU must be reduced to 95 grams per kilometer; the US carbon dioxide emissions must be reduced to 97 grams per kilometer by 2025; Japan must be reduced to 97 grams per kilometer by 2020 Reduced to 122 grams. my country's "Energy-saving and New Energy Automobile Industry Development Plan (2012-2020)" clearly states that in 2020, the average fuel consumption of traditional fuel-fueled passenger cars will be reduced to 5.0L/100km, and the average fuel consumption of new energy-saving passenger cars will be reduced to 4.5L /100km or less. According to a survey conducted by the Lithium Battery Research Institute of Gaogong Industrial Research Institute, the automobile lithium-ion start-stop system saves fuel by more than 8% in urban road conditions, and can reduce CO 2 emissions, and can start the car quickly and safely. Therefore, the lithium-ion start-stop power supply has become a main engine factory. One of the effective means to reduce fuel consumption.
锂离子启停电源在功率密度、倍率性能等方面都有很高的技术要求，需要克服在低温下大电流放电、高温下运行稳定性及存储稳定性等难点，较高的技术门槛需要电池企业从电池关键材料着手提升锂离子启停电源的整体性能。硬碳是锂离子电池内的常用的一种电极材料，且颇具市场前景。其有着大倍率的充放电能量，即使在低温下，也可展现其快速的嵌锂能力。然而制约其发展的是其作为电源负极，存在非常低的首次充放电效率，仅约80％。Lithium-ion start-stop power supplies have high technical requirements in terms of power density, rate performance, etc., and need to overcome difficulties such as high current discharge at low temperatures, operation stability at high temperatures, and storage stability. Higher technical thresholds require battery companies. Start with the key battery materials to improve the overall performance of the lithium-ion start-stop power supply. Hard carbon is a commonly used electrode material in lithium-ion batteries, and has considerable market prospects. It has a large rate of charge and discharge energy, even at low temperatures, it can also show its rapid lithium insertion ability. However, what restricts its development is that as the negative electrode of the power supply, it has a very low first charge and discharge efficiency, only about 80%.
Li 5FeO 4是一种新近报道的非常理想的锂源材料，理论上每摩尔的Li 5FeO 4可以提供5个锂离子，其比容量贡献可达到867mAh/g。其作为正极锂源能在首次充电时释放大量锂离子，显著的提高电源的首次效率，电极反应如下： Li 5 FeO 4 is a recently reported ideal lithium source material. In theory, each mole of Li 5 FeO 4 can provide 5 lithium ions, and its specific capacity contribution can reach 867 mAh/g. As a positive electrode lithium source, it can release a large amount of lithium ions during the first charge, which significantly improves the first efficiency of the power supply. The electrode reaction is as follows:
Li 5FeO 4→4Li ++4e -+LiFeO 2+O 2 Li 5 FeO 4 → 4Li + + 4e - + LiFeO 2 + O 2
释放锂离子后的产物活性极低，不会发生再次嵌锂或者溶解。而对于锂离子启停电源正极，镍钴锰三元材料则最为常见，此材料通过Ni-Co-Mn的协同作用，结合了LiCoO 2循环性能好、LiNiO 2高比容量和LiMnO 2成本低安全性能好的优点，是目前锂离子电池正极材料的主流，其在电池比能量、比功率、大倍率充电、低温性能等方面有优势。 The activity of the product after the release of lithium ions is extremely low, and there will be no re-intercalation or dissolution of lithium. For lithium ion start-stop power supply cathodes, nickel-cobalt-manganese ternary materials are the most common. This material combines the synergistic effect of Ni-Co-Mn and combines good cycle performance of LiCoO 2 , high specific capacity of LiNiO 2 and low cost and safety of LiMnO 2 The advantages of good performance are currently the mainstream of lithium-ion battery cathode materials, which have advantages in battery specific energy, specific power, high-rate charging, and low-temperature performance.
预锂化是指对全电池而言，化成时负极界面形成的SEI膜会消耗掉从正极脱嵌的锂离子，并降低电池的容量。如果可以从正极材料外再寻找到一个锂源，让SEI膜的形成消耗外界锂源的锂离子，这样就可以保证正极脱嵌的锂离子不会浪费于化成过程，最终就可以提高全电池容量。这个提供外界锂源的过程，就是预锂化。Pre-lithiation means that for a full battery, the SEI film formed at the negative electrode interface will consume the lithium ions extracted from the positive electrode and reduce the battery capacity. If a lithium source can be found outside the cathode material, the formation of the SEI film will consume the lithium ions of the external lithium source, so that the lithium ions deintercalated from the cathode will not be wasted in the formation process, and the full battery capacity can be increased. . This process of providing an external lithium source is pre-lithiation.
现有技术中，如美国专利US 20160372784 A1，“Cathode Additives to Provide an Excess Lithium Source for Lithium Ion Batteries”描述了锂离子电池正极中所使用的一系列可以提供额外锂源的试剂，其中包括了Li 5FeO 4。其与本发明的主要区别是本发明是直接合成了包含Li 5FeO 4的正极复合材料。中国专利CN 106601489 A，“一种无需预嵌锂型锂离子电容器及其制备方法”描述了一种无需预嵌锂型电容器及其制备方法，属于电容器技术领域。其主要内容为其发明了多孔碳/Li 5FeO 4复合材料，作为正极材料。与本发明的主要区别为1.本发明领域为锂离子启停电源领域；2.本发明中的复合材料为LiNi xCo yMn zO 2/Li 5FeO 4复合材料。美国专利US 8313721 B2，“Lithium-oxygen(AIR)electrochemical cells and batteries”描述了一种锂空气电池，其中涉及到了Li 5FeO 4材料，但与本发明属于不同的技术领域不同，其发明内容也与本发明没有关联。美国专利US20150050561A1，“High voltage lithium ion batteries having fluorinated electrolytes and lithium-based additives”描述了一种高电压的锂离子电池。其与本发明不同的是：1.发明领域，此专利领域为高电压的锂离子电池，4.6V；而本发明则是锂离子启停电源领域；2.在此专利中，Li 5FeO 4本身作为其添加剂；3.其活性物质不包括LiNi xCo yMn zO 2/Li 5FeO 4复合材料。中国专利CN103700848A，“一种锂离子电池正极材料、正极及电池”，描述了一种锂离子电池，与本发明不同的则是，其涉及的正极材料为LiFePO 4，而Li 5FeO 4材料作 为电池添加剂。关于现有技术，目前还没有公开使用三元镍钴锰材料与Li 5FeO 4材料进行复合制成LiNi xCo yMn zO 2/Li 5FeO 4复合材料，并将该复合材料应用于启停电源技术领域以获得具有优良性能的启停电源的相关技术。 In the prior art, for example, US Patent US 20160372784 A1, "Cathode Additives to Provide an Excess Lithium Source for Lithium Ion Batteries" describes a series of reagents used in the positive electrode of lithium ion batteries that can provide additional lithium sources, including Li 5 FeO 4 . The main difference between it and the present invention is that the present invention directly synthesizes a positive electrode composite material containing Li 5 FeO 4. Chinese patent CN 106601489 A, "A lithium ion capacitor without pre-insertion and its preparation method" describes a lithium-ion capacitor without pre-insertion and its preparation method, and belongs to the technical field of capacitors. The main content is that he invented a porous carbon/Li 5 FeO 4 composite material as a positive electrode material. The main difference from the present invention is 1. The field of the present invention is the field of lithium ion start-stop power supplies; 2. The composite material in the present invention is LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material. US patent US 8313721 B2, "Lithium-oxygen (AIR) electrochemical cells and batteries" describes a lithium-air battery, which involves Li 5 FeO 4 material, but it belongs to a different technical field from the present invention, and its content is also It is not related to the present invention. US patent US20150050561A1, "High voltage lithium ion batteries having fluorinated electrolytes and lithium-based additives" describes a high voltage lithium ion battery. The difference from the present invention is: 1. The field of invention, this patent field is a high-voltage lithium ion battery, 4.6V; while the present invention is in the field of lithium ion start-stop power supplies; 2. In this patent, Li 5 FeO 4 As its additive; 3. Its active material does not include LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material. Chinese Patent CN103700848A, "A Lithium-ion Battery Cathode Material, Cathode and Battery", describes a lithium-ion battery. The difference from the present invention is that the cathode material involved is LiFePO 4 , and the Li 5 FeO 4 material is used as Battery additives. Regarding the prior art, there is currently no disclosure of using ternary nickel-cobalt-manganese materials and Li 5 FeO 4 materials to make LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite materials, and applying the composite materials to Kai In the field of power-off technology, related technologies to obtain power-off power with excellent performance.
基于以上，期待一种性能优良的可预锂化的锂离子启停电源及其制备方法，其电极所用材料是通过将三元镍钴锰材料与Li 5FeO 4材料进行复合而制成的LiNi xCo yMn zO 2/Li 5FeO 4复合材料，此复合材料作为电极组正极与硬碳负极共同制备锂离子启停电源，其电化学性能较目前商业化锂离子启停电源相比具有明显的优势。 Based on the above, expect a lithium ion start-stop power supply with excellent performance that can be prelithiated and a preparation method thereof. The electrode material is LiNi made by compounding a ternary nickel-cobalt-manganese material with a Li 5 FeO 4 material. x Co y Mn z O 2 /Li 5 FeO 4 composite material. This composite material is used as the positive electrode of the electrode group and the hard carbon negative electrode to prepare a lithium ion start-stop power supply. Its electrochemical performance is better than that of the current commercial lithium-ion start-stop power supply. obvious advantage.
发明内容Summary of the invention
本发明的目的就是为了解决现有的锂离子启停电源的比能量、比功率、充放电次数低、低温性能差等的缺陷，从而提供一种可预锂化的锂离子启停电源及其制备方法，根据本发明的方法制备得到的锂离子启停电源具有高功率高首次效率以及好的低温特性。The purpose of the present invention is to solve the shortcomings of the existing lithium ion start-stop power supply such as specific energy, specific power, low charge and discharge times, poor low-temperature performance, etc., so as to provide a pre-lithiated lithium-ion start-stop power supply and the same The preparation method, the lithium ion start-stop power supply prepared according to the method of the present invention has high power, high first-time efficiency and good low temperature characteristics.
本发明的目的及解决其技术问题采用以下的技术方案来实现：The purpose of the present invention and the solution of its technical problems are achieved by adopting the following technical solutions:
本发明的一个实施方式提供了一种可预锂化的锂离子启停电源，包括正极和负极，其中，所述正极主要由LiNi xCo yMn zO 2/Li 5FeO 4复合材料制成，其中x+y+z＝1。 An embodiment of the present invention provides a prelithiated lithium ion start-stop power supply, including a positive electrode and a negative electrode, wherein the positive electrode is mainly made of LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material , Where x+y+z=1.
根据本发明的上述一个实施方式提供的一种可预锂化的锂离子启停电源，其中，所述Li 5FeO 4是通过将Li 2O与Fe 2O 3按摩尔比为5:1的量机械混合，压制成片，最后在高温下烧结而制成。 According to the above-mentioned one embodiment of the present invention, there is provided a pre-lithiated lithium ion start-stop power supply, wherein the Li 5 FeO 4 is made by mixing Li 2 O and Fe 2 O 3 at a molar ratio of 5:1. The amount is mechanically mixed, pressed into tablets, and finally sintered at high temperature to produce.
根据本发明的上述一个实施方式提供的一种可预锂化的锂离子启停电源，其中，所述LiNi xCo yMn zO 2/Li 5FeO 4复合材料是通过将LiNi xCo yMn zO 2和Li 5FeO 4按质量比为(0.8～0.98):(0.02～0.2)的量混合后经球磨而制成。 According to the above-mentioned one embodiment of the present invention, there is provided a lithium ion start-stop power supply capable of pre-lithiation, wherein the LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material is obtained by combining LiNi x Co y Mn z O 2 and Li 5 FeO 4 are mixed in a mass ratio of (0.8～0.98):(0.02～0.2) and then ball milled.
根据本发明的上述一个实施方式提供的一种可预锂化的锂离子启停电源，其中，所述LiNi xCo yMn zO 2选自LiNi 1/3Co 1/3Mn 1/3O 2、LiNi 0.5Co 0.2Mn 0.3O 2、LiNi 0.6Co 0.2Mn 0.2O 2、LiNi 0.8Co 0.1Mn 0.1O 2中的一种或多种。 According to the above-mentioned one embodiment of the present invention, a lithium ion start-stop power supply capable of prelithiation is provided, wherein the LiNi x Co y Mn z O 2 is selected from LiNi 1/3 Co 1/3 Mn 1/3 O 2. One or more of LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 .
本发明的另一个实施方式还提供了一种制备上述可预锂化的锂离子启停电源的方法，其中，该方法包括以下步骤：Another embodiment of the present invention also provides a method for preparing the above-mentioned prelithiated lithium ion start-stop power supply, wherein the method includes the following steps:
(1)制备LiNi xCo yMn zO 2/Li 5FeO 4复合材料； (1) Preparation of LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material;
(2)将得到的LiNi xCo yMn zO 2/Li 5FeO 4复合材料、粘结剂、导电剂混合均匀后加入溶剂搅拌2～5h，得到的浆料涂覆于铝箔上成型，制备得复合材料电极，将复合电极材料经先烘干再碾压成片后切成带有极耳的正极片成品； (2) Mix the obtained LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material, binder, and conductive agent uniformly, add the solvent and stir for 2 to 5 hours, and coat the obtained slurry on aluminum foil for forming. To obtain a composite electrode, the composite electrode material is dried and then rolled into a sheet, and then cut into a positive electrode sheet with tabs;
(3)将石墨或硬碳、粘结剂、导电剂混合均匀后加入溶剂搅拌2～5h，得到的浆料涂覆于铜箔上成型，制备得到碳电极，将碳电极经先烘干再碾压成片后切成带有极耳的负极片成品；(3) Mix the graphite or hard carbon, the binder, and the conductive agent evenly, then add the solvent and stir for 2 to 5 hours, and the slurry obtained is coated on the copper foil to form a carbon electrode. The carbon electrode is dried and then After rolling into pieces, cut into finished negative pieces with tabs;
(4)分别将步骤(2)和(3)得到的电极片成品作为正负极，以PP/PE复合微孔膜为隔膜，进行叠片并联完成极耳的焊接得到电极组；(4) The finished electrode sheets obtained in steps (2) and (3) are used as positive and negative electrodes, and the PP/PE composite microporous membrane is used as the diaphragm, and the electrodes are stacked in parallel to complete the welding of the tabs to obtain an electrode group;
(5)将电极组放入铝塑膜包装袋中，以含1M的LiPF6的碳酸乙烯酯:碳酸甲乙酯＝6:4为电解液，在露点-45℃～-40℃的条件下完成注液及一次封口，即得到锂离子启停电源。(5) Put the electrode group into an aluminum plastic film packaging bag, use 1M LiPF6 ethylene carbonate: ethyl methyl carbonate = 6:4 as the electrolyte, and complete it under the condition of dew point -45℃～-40℃ Liquid injection and one-time sealing, the lithium ion start-stop power supply is obtained.
根据本发明的上述一个实施方式提供的一种可预锂化的启停电源的制备方法，其中，所述步骤(1)中，所述LiNi xCo yMn zO 2/Li 5FeO 4复合材料是由以下步骤制备而成： According to the above-mentioned one embodiment of the present invention, there is provided a method for preparing a pre-lithiated start-stop power supply, wherein, in the step (1), the LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite The material is prepared by the following steps:
a.将Li 2O和Fe 2O 3混合后压制成片并在700～900℃的条件下烧结15～25h得到Li 5FeO 4材料。 a. After mixing Li 2 O and Fe 2 O 3, they are pressed into tablets and sintered at 700-900° C. for 15-25 hours to obtain Li 5 FeO 4 materials.
b.将得到的Li 5FeO 4和LiNi xCo yMn zO 2混合后进行球磨，之后过筛即得到LiNi xCo yMn zO 2/Li 5FeO 4复合材料。 b. The obtained Li 5 FeO 4 and LiNi x Co y Mn z O 2 are mixed and ball milled, and then sieved to obtain a LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material.
根据本发明的上述一个实施方式提供的一种可预锂化的启停电源的制备方法，其中，所述步骤a中，所述Li 2O和Fe 2O 3的摩尔比为5:1。 According to the above-mentioned one embodiment of the present invention, there is provided a method for preparing a pre-lithiated start-stop power supply, wherein, in the step a, the molar ratio of Li 2 O and Fe 2 O 3 is 5:1.
根据本发明的上述一个实施方式提供的一种可预锂化的启停电源的制备方法，其中，所述步骤b中，所述LiNi xCo yMn zO 2和Li 5FeO 4的质量比为(0.8～0.98):(0.02～0.2)。 According to the above-mentioned one embodiment of the present invention, there is provided a method for preparing a pre-lithiated start-stop power supply, wherein, in the step b, the mass ratio of the LiNi x Co y Mn z O 2 and Li 5 FeO 4 It is (0.8～0.98):(0.02～0.2).
根据本发明的上述一个实施方式提供的一种可预锂化的启停电源的制备方法，其中，所述LiNi xCo yMn zO 2满足x+y+z＝1，可选自LiNi 1/3Co 1/3Mn 1/3O 2、LiNi 0.5Co 0.2Mn 0.3O 2、LiNi 0.6Co 0.2Mn 0.2O 2、LiNi 0.8Co 0.1Mn 0.1O 2中的一种或多种。 According to the above-mentioned one embodiment of the present invention, there is provided a method for preparing a pre-lithiated start-stop power supply, wherein the LiNi x Co y Mn z O 2 satisfies x+y+z=1 and can be selected from LiNi 1 One or more of /3 Co 1/3 Mn 1/3 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiNi 0.6 Co 0.2 Mn 0.2 O 2 , and LiNi 0.8 Co 0.1 Mn 0.1 O 2 .
根据本发明的上述一个实施方式提供的一种可预锂化的启停电源的制备方法，其中，所述步骤b中，所述LiNi xCo yMn zO 2/Li 5FeO 4复合材料是通过将Li 5FeO 4和LiNi xCo yMn zO 2混合后放入内衬为氧化锆材料的球磨罐中，以高纯氧化锆球为球磨介质，按照球料重量比为60:1，在转速为300～600rmp/min的条件下球磨2～24h后过筛而得到的。 According to the above-mentioned one embodiment of the present invention, there is provided a method for preparing a pre-lithiated start-stop power supply, wherein, in the step b, the LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material is By mixing Li 5 FeO 4 and LiNi x Co y Mn z O 2 into a ball milling tank lined with zirconia material, using high-purity zirconia balls as the ball milling medium, the weight ratio of the balls is 60:1. It is obtained by sieving after ball milling for 2-24h under the condition of rotating speed of 300-600rmp/min.
根据本发明的上述一个实施方式提供的一种可预锂化的启停电源的制备方法，其中，所述步骤(2)中，所述LiNi xCo yMn zO 2/Li 5FeO 4复合材料、粘结剂、导电剂的质量比为(80～98):(1～5):(0.5～10)。 According to the above-mentioned one embodiment of the present invention, a method for preparing a pre-lithiated start-stop power supply is provided, wherein, in the step (2), the LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite The mass ratio of material, binder, and conductive agent is (80～98):(1～5):(0.5～10).
根据本发明的上述一个实施方式提供的一种可预锂化的启停电源的制备方法，其中，所述步骤(2)中，所述粘结剂为质量分数为2％～10％的PVDF溶液；所述溶剂为NMP溶液，其按固含量40％～70％的量加入。According to the above-mentioned one embodiment of the present invention, there is provided a method for preparing a pre-lithiated start-stop power supply, wherein, in the step (2), the binder is PVDF with a mass fraction of 2%-10% Solution; The solvent is an NMP solution, which is added at a solid content of 40% to 70%.
根据本发明的上述一个实施方式提供的一种可预锂化的启停电源的制备方法，其中，所述步骤(3)中，所述石墨或硬碳、粘结剂、导电剂的质量比为(80～98):(1～5):(0.5～8)。According to the above-mentioned one embodiment of the present invention, a method for preparing a pre-lithiated start-stop power supply is provided, wherein, in the step (3), the mass ratio of the graphite or hard carbon, the binder, and the conductive agent is It is (80～98):(1～5):(0.5～8).
根据本发明的上述一个实施方式提供的一种可预锂化的启停电源的制备方法，其中，所述步骤(3)中，所述粘结剂为丙烯腈多元共聚物、羟甲基纤维素、丁苯橡胶中的一种或多种；所述溶剂为水，其按固含量40％～70％的量加入。According to the above-mentioned one embodiment of the present invention, a method for preparing a pre-lithiated start-stop power supply is provided, wherein, in the step (3), the binder is an acrylonitrile multi-element copolymer, a methylol fiber One or more of vegetable and styrene-butadiene rubber; the solvent is water, which is added at a solid content of 40% to 70%.
根据本发明的上述一个实施方式提供的一种可预锂化的启停电源的制备方法，其中，所述导电剂选自炭黑、导电石墨、碳纤维、碳纳米管中的一种或多种。According to the above-mentioned one embodiment of the present invention, there is provided a method for preparing a pre-lithiated start-stop power supply, wherein the conductive agent is selected from one or more of carbon black, conductive graphite, carbon fiber, and carbon nanotube .
根据本发明的实施方式提供的可预锂化的锂离子启停电源及其制备方法的优点在于：The advantages of the pre-lithiated lithium ion start-stop power supply and the preparation method thereof provided by the embodiments of the present invention are:
(1)本发明所使用的制备锂离子启停电源正极材料为 LiNi xCo yMn zO 2/Li 5FeO 4复合材料，该复合材料是以锂离子电池商业化过渡金属氧化物正极材料LiNi xCo yMn zO 2为基础(其中x+y+z＝1)，通过与由Li 2O与Fe 2O 3所合成的Li 5FeO 4球磨混合制成，过程简单，成本较低，易于实现工业化生产。 (1) The lithium ion start-stop power supply cathode material used in the present invention is LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material, which is a lithium ion battery commercial transition metal oxide cathode material LiNi Based on x Co y Mn z O 2 (where x+y+z=1), it is made by ball milling and mixing with Li 5 FeO 4 synthesized by Li 2 O and Fe 2 O 3. The process is simple and the cost is low. It is easy to realize industrialized production.
(2)LiNi xCo yMn zO 2/Li 5FeO 4复合材料能够同时结合LiNi xCo yMn zO 2具有优良的电池比能量、比功率、大倍率充电、低温性能以及Li 5FeO 4具有高的比容量、显著的首次效率的优势，所制备得到的锂离子启停电源经组装测试，具有高功率高首次效率以及良好的低温特性，其首次效率最高可达90％～92％，测试其倍率性能，电源在超大倍率，如40C，可实现连续放电，放电容量可达初始容量的79.5％；通过测试软包电芯的低温性能，其在-20℃下，可实现大倍率放电，如20C倍率放电，容量可达初始容量的51.6％。 (2) The LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material can simultaneously combine with LiNi x Co y Mn z O 2 and has excellent battery specific energy, specific power, high rate charging, low temperature performance and Li 5 FeO 4 It has the advantages of high specific capacity and significant first-time efficiency. The prepared lithium-ion start-stop power supply has high power, high first-time efficiency and good low-temperature characteristics after assembly and testing, and its first-time efficiency can reach 90% to 92%. Test its rate performance, the power supply can achieve continuous discharge at a super-high rate, such as 40C, and the discharge capacity can reach 79.5% of the initial capacity; by testing the low-temperature performance of the soft-packed cell, it can achieve high-rate discharge at -20°C , Such as 20C rate discharge, the capacity can reach 51.6% of the initial capacity.
(3)本发明提供的启停电源的制备方法工艺简单，整个过程与目前电池工业化生产过程类似，具有成本低、易于实现工业化的优势。(3) The preparation method of the start-stop power supply provided by the present invention has a simple process, and the whole process is similar to the current battery industrial production process, and has the advantages of low cost and easy realization of industrialization.
附图说明Description of the drawings
图1为根据本发明的实施例1中制备的可预锂化的锂离子启停电源室温倍率性能测试图；Fig. 1 is a room temperature rate performance test diagram of a prelithiated lithium ion start-stop power supply prepared in Example 1 of the present invention;
图2为根据本发明的实施例1中制备的可预锂化的锂离子启停电源室温下容量-电流性能曲线；Fig. 2 is a capacity-current performance curve at room temperature of a prelithiated lithium ion start-stop power supply prepared in Example 1 of the present invention;
图3为根据本发明的实施例1中制备的可预锂化的锂离子启停电源-20℃低温性能测试图。Fig. 3 is a low-temperature performance test diagram of a lithium ion start-stop power supply capable of pre-lithiation prepared in Example 1 according to the present invention at -20°C.
具体实施方式Detailed ways
下面结合附图和实施例对本发明作进一步的阐述，应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后本领域技术人员可以对本发明做各种改动或修改，这些等价同样落于本申请所附权利要求书所限定的范围。The present invention will be further described below in conjunction with the accompanying drawings and embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalents also fall within the scope defined by the appended claims of the present application.
实施例1Example 1
将Li 2O与Fe 2O 3按5:1的摩尔比机械混合后压制成片，并在850℃下烧结20小时，得到Li 5FeO 4材料。之后，将LiNi 0.6Co 0.2Mn 0.2O 2(购自北京当升材料科技股份有限公司，中国)与得到的Li 5FeO 4材料，在干燥的环境中，按照质量比LiNi 0.6Co 0.2Mn 0.2O 2：Li 5FeO 4＝9：1的量混合后与氧化锆球按照球料重量比为60:1一同放入内衬为氧化锆材料的球磨罐内，在转速为500rmp/min的条件下干法球磨8h，之后过筛即得到LiNi 0.6Co 0.2Mn 0.2O 2/Li 5FeO 4复合材料。 Li 2 O and Fe 2 O 3 were mechanically mixed at a molar ratio of 5:1 and then pressed into tablets, and sintered at 850° C. for 20 hours to obtain Li 5 FeO 4 materials. After that, the LiNi 0.6 Co 0.2 Mn 0.2 O 2 (purchased from Beijing Dangsheng Material Technology Co., Ltd., China) and the obtained Li 5 FeO 4 material, in a dry environment, according to the mass ratio of LiNi 0.6 Co 0.2 Mn 0.2 O 2 : Li 5 FeO 4 ＝9:1, mix with zirconia balls according to the ball weight ratio of 60:1 and put them into a ball milling tank lined with zirconia material at a speed of 500rmp/min Dry ball milling for 8 hours, then sieving to obtain LiNi 0.6 Co 0.2 Mn 0.2 O 2 /Li 5 FeO 4 composite material.
将得到的LiNi 0.6Co 0.2Mn 0.2O 2/Li 5FeO 4复合材料、PVDF和炭黑按质量比92：5：3混合均匀后按固含量50％的量加入NMP溶剂搅拌3.5h，所得的浆料均匀涂覆于双面铝箔上成型，制备得复合材料电极，将复合电极材料经先烘干再碾压成片后切成带有极耳的正极片(5.9cm×10.9cm)成品若干。 The obtained LiNi 0.6 Co 0.2 Mn 0.2 O 2 /Li 5 FeO 4 composite material, PVDF and carbon black were mixed uniformly at a mass ratio of 92:5:3, and then NMP solvent was added at a solid content of 50% and stirred for 3.5 hours. The slurry is uniformly coated on double-sided aluminum foil to form a composite electrode. The composite electrode material is dried and then rolled into a sheet and then cut into a positive electrode sheet (5.9cm×10.9cm) with tabs (5.9cm×10.9cm). Several finished products .
将硬碳材料、LA132、炭黑按质量比为94：3：3混合均匀后按固含量50％的量加入去离子水搅拌3.5h，所得的浆料均匀涂于双面铜箔上成型，制备得到碳电极，将碳电极经先烘干再碾压成片后切成带有极耳的负极片(6.0cm×11.0cm)成品若干。Mix the hard carbon material, LA132, and carbon black at a mass ratio of 94:3:3, then add deionized water at a solid content of 50% and stir for 3.5 hours. The resulting slurry is evenly coated on double-sided copper foil for molding. The carbon electrode is prepared, and the carbon electrode is dried and then rolled into a sheet, and then cut into a negative electrode sheet (6.0cm×11.0cm) with tabs (6.0cm×11.0cm).
将上述所制得的正负极电极片，以PP/PE复合微孔膜为隔膜，按照10片正极片、11片负极片进行叠片并联完成极耳焊接得到电极组。The positive and negative electrode sheets prepared above, using the PP/PE composite microporous membrane as the separator, are laminated in parallel according to 10 positive sheets and 11 negative sheets to complete the tab welding to obtain an electrode group.
将电极组放入铝塑膜包装袋中，以含1M的LiPF 6的碳酸乙烯酯:碳酸甲乙酯＝6:4为电解液，在露点-45℃的条件下完成注液以及一次封口，即得到可预锂化的锂离子启停电源。 Put the electrode group into an aluminum-plastic film packaging bag, use 1M LiPF 6 ethylene carbonate: ethyl methyl carbonate = 6:4 as the electrolyte, and complete the injection and one-time sealing under the condition of -45°C dew point. That is, a lithium ion start-stop power supply capable of pre-lithiation is obtained.
图1为根据本发明的实施例1中制备的锂离子启停电源室温倍率性能测试；图2为根据本发明的实施例1中制备的锂离子启停电源室温下容量-电流性能曲线。如图1和图2所示，所制得的锂离子启停电源其首次效率为90％～92％，测试其倍率性能，电源在超大倍率，如40C倍率下，也可实现连续放电，放电容量可达初始容量的79.5％。图3为根据本发明的实施例1中制备的锂离子启停电源-20℃低温性能测试图。如图3所示，通过测试该锂离子启停电源的低温性能，其在-20℃下，可实现大倍率放电，如在20C倍率放电下，容 量可达初始容量的51.6％。对其500cy循环性能测定，可达到96.3％。Fig. 1 is a room temperature magnification performance test of a lithium-ion start-stop power supply prepared in Example 1 of the present invention; Fig. 2 is a room temperature capacity-current performance curve of a lithium-ion start-stop power supply prepared in Example 1 of the present invention. As shown in Figure 1 and Figure 2, the first efficiency of the lithium ion start-stop power supply prepared is 90% to 92%. The rate performance is tested. The power supply can also achieve continuous discharge and discharge at a super-large rate, such as 40C. The capacity can reach 79.5% of the initial capacity. Fig. 3 is a low-temperature performance test diagram of the lithium ion start-stop power supply prepared in Example 1 according to the present invention at -20°C. As shown in Figure 3, by testing the low-temperature performance of the lithium-ion start-stop power supply, it can achieve large-rate discharge at -20°C. For example, under 20C-rate discharge, the capacity can reach 51.6% of the initial capacity. The test of its 500cy cycle performance can reach 96.3%.
实施例2Example 2
将Li 2O与Fe 2O 3按5:1的摩尔比机械混合后压制成片，并在900℃下烧结25小时，得到Li 5FeO 4材料。之后，将LiNi 0.5Co 0.2Mn 0.3O 2(购自北京当升材料科技股份有限公司，中国)与得到的Li 5FeO 4材料，在干燥的环境中，按照质量比LiNi 0.5Co 0.2Mn 0.3O 2：Li 5FeO 4＝9.8：0.2的量混合后与氧化锆球按照球料重量比为60:1一同放入内衬为氧化锆材料的球磨罐内，在转速为600rmp/min的条件下干法球磨13h，之后过筛即得到LiNi 0.5Co 0.2Mn 0.3O 2/Li 5FeO 4复合材料。 Li 2 O and Fe 2 O 3 were mechanically mixed at a molar ratio of 5:1 and then pressed into tablets, and sintered at 900° C. for 25 hours to obtain Li 5 FeO 4 materials. After that, LiNi 0.5 Co 0.2 Mn 0.3 O 2 (purchased from Beijing Dangsheng Material Technology Co., Ltd., China) and the obtained Li 5 FeO 4 material were combined in a dry environment according to the mass ratio of LiNi 0.5 Co 0.2 Mn 0.3 O 2 : Li 5 FeO 4 =9.8:0.2 and mixed with zirconia balls according to the ball weight ratio of 60:1 and put them into a ball milling tank lined with zirconia material at a speed of 600rmp/min Dry ball milling for 13 hours, then sieving to obtain LiNi 0.5 Co 0.2 Mn 0.3 O 2 /Li 5 FeO 4 composite material.
将得到的LiNi 0.5Co 0.2Mn 0.3O 2/Li 5FeO 4复合材料、PVDF和炭黑按质量比85：5：10混合均匀后按固含量70％的量加入NMP溶剂搅拌5h，所得的浆料均匀涂覆于双面铝箔上成型，制备得复合材料电极，将复合电极材料经先烘干再碾压成片后切成带有极耳的正极片(5.9cm×10.9cm)成品若干。 The obtained LiNi 0.5 Co 0.2 Mn 0.3 O 2 /Li 5 FeO 4 composite material, PVDF and carbon black were mixed uniformly at a mass ratio of 85:5:10, and then NMP solvent was added at a solid content of 70% and stirred for 5 hours. The resulting slurry The material is uniformly coated on double-sided aluminum foil to form a composite electrode. The composite electrode material is dried and then rolled into a sheet, and then cut into a positive electrode sheet (5.9cm×10.9cm) with tabs (5.9cm×10.9cm).
将硬碳材料、羟甲基纤维素和丁苯橡胶、炭黑和碳纤维按质量比为87：5：8混合均匀后按固含量40％的量加入去离子水搅拌5h，所得的浆料均匀涂于双面铜箔上成型，制备得到碳电极，将碳电极经先烘干再碾压成片后切成带有极耳的负极片(6.0cm×11.0cm)成品若干。Mix the hard carbon material, hydroxymethyl cellulose and styrene butadiene rubber, carbon black and carbon fiber at a mass ratio of 87:5:8, and then add deionized water at a solid content of 40% and stir for 5 hours. The resulting slurry is uniform It is coated on double-sided copper foil to form a carbon electrode. The carbon electrode is dried and then rolled into a sheet, and then cut into a negative electrode sheet (6.0cm×11.0cm) with tabs (6.0cm×11.0cm).
将上述所制得的正负极电极片，以PP/PE复合微孔膜为隔膜，按照10片正极片、11片负极片进行叠片并联完成极耳焊接得到电极组。The positive and negative electrode sheets prepared above, using the PP/PE composite microporous membrane as the separator, are laminated in parallel according to 10 positive sheets and 11 negative sheets to complete the tab welding to obtain an electrode group.
将电极组放入铝塑膜包装袋中，以含1M的LiPF 6的碳酸乙烯酯:碳酸甲乙酯＝6:4为电解液，在露点-45℃的条件下完成注液以及一次封口，即得到可预锂化的锂离子启停电源。 Put the electrode group into an aluminum-plastic film packaging bag, use 1M LiPF 6 ethylene carbonate: ethyl methyl carbonate = 6:4 as the electrolyte, and complete the injection and one-time sealing under the condition of -45°C dew point. That is, a lithium ion start-stop power supply capable of pre-lithiation is obtained.
所制得的锂离子启停电源其首次效率为85％～87％，测试其倍率性能，电源在超大倍率，如40C倍率下，也可实现连续放电，放电容量可达初始容量的75.3％；通过测试该锂离子启停电源的低温性能，其在-20℃下，可实现大倍率放电，如在20C倍率放电下，容量可达初始容量的49.6％；对其500cy循环性能测定，可达到95.7％。The prepared lithium-ion start-stop power supply has an initial efficiency of 85% to 87%. The rate performance is tested. The power supply can also achieve continuous discharge at a super-large rate, such as a 40C rate, and the discharge capacity can reach 75.3% of the initial capacity; By testing the low-temperature performance of the lithium-ion start-stop power supply, it can achieve large-rate discharge at -20°C. For example, under 20C-rate discharge, the capacity can reach 49.6% of the initial capacity; the 500cy cycle performance measurement can reach 95.7%.
实施例3Example 3
将Li 2O与Fe 2O 3按5:1的摩尔比机械混合后压制成片，并在700℃下烧结15小时，得到Li 5FeO 4材料。之后，将LiNi 1/3Co 1/3Mn 1/3O 2(购自北京当升材料科技股份有限公司，中国)与得到的Li 5FeO 4材料，在干燥的环境中，按照质量比LiNi 1/3Co 1/3Mn 1/3O 2：Li 5FeO 4＝9：1的量混合后与氧化锆球按照球料重量比为60:1一同放入内衬为氧化锆材料的球磨罐内，在转速为300rmp/min的条件下干法球磨2h，之后过筛即得到LiNi 1/3Co 1/3Mn 1/3O 2/Li 5FeO 4复合材料。 Li 2 O and Fe 2 O 3 were mechanically mixed at a molar ratio of 5:1 and then pressed into tablets, and sintered at 700° C. for 15 hours to obtain Li 5 FeO 4 materials. After that, the LiNi 1/3 Co 1/3 Mn 1/3 O 2 (purchased from Beijing Dangsheng Material Technology Co., Ltd., China) and the obtained Li 5 FeO 4 material, in a dry environment, according to the mass ratio of LiNi 1/3 Co 1/3 Mn 1/3 O 2 ：Li 5 FeO 4 ＝9:1, mix with zirconia balls in a ball mill lined with zirconia at a weight ratio of 60:1 In the tank, dry ball milling for 2 hours at a speed of 300 rpm/min, and then sieving to obtain a LiNi 1/3 Co 1/3 Mn 1/3 O 2 /Li 5 FeO 4 composite material.
将得到的LiNi 1/3Co 1/3Mn 1/3O 2/Li 5FeO 4复合材料、PVDF、炭黑和导电石墨按质量比98：1：1混合均匀后按固含量40％的量加入NMP溶剂搅拌2h，所得的浆料均匀涂覆于双面铝箔上成型，制备得复合材料电极，将复合电极材料经先烘干再碾压成片后切成带有极耳的正极片(5.9cm×10.9cm)成品若干。 The obtained LiNi 1/3 Co 1/3 Mn 1/3 O 2 /Li 5 FeO 4 composite material, PVDF, carbon black and conductive graphite are mixed uniformly at a mass ratio of 98:1:1, and then the solid content is 40%. Add NMP solvent and stir for 2 hours. The resulting slurry is evenly coated on double-sided aluminum foil to form a composite electrode. The composite electrode material is dried and then rolled into a sheet and then cut into a positive electrode sheet with tabs ( 5.9cm×10.9cm) several finished products.
将石墨材料、羟甲基纤维素和丁苯橡胶、炭黑按质量比为91：1：8混合均匀后按固含量70％的量加入去离子水搅拌2h，所得的浆料均匀涂于双面铜箔上成型，制备得到碳电极，将碳电极经先烘干再碾压成片后切成带有极耳的负极片(6.0cm×11.0cm)成品若干。The graphite material, hydroxymethyl cellulose, styrene-butadiene rubber, and carbon black are mixed uniformly in a mass ratio of 91:1:8, and then deionized water is added at a solid content of 70% and stirred for 2 hours. The resulting slurry is evenly coated on the double The carbon electrode is prepared by forming on the copper foil. The carbon electrode is dried and then rolled into a sheet, and then cut into a negative sheet (6.0cm×11.0cm) with tabs (6.0cm×11.0cm).
将上述所制得的正负极电极片，以PP/PE复合微孔膜为隔膜，按照10片正极片、11片负极片进行叠片并联完成极耳焊接得到电极组。The positive and negative electrode sheets prepared above, using the PP/PE composite microporous film as the separator, are laminated in parallel according to 10 positive sheets and 11 negative sheets to complete the tab welding to obtain an electrode group.
将电极组放入铝塑膜包装袋中，以含1M的LiPF 6的碳酸乙烯酯:碳酸甲乙酯＝6:4为电解液，在露点-40℃的条件下完成注液以及一次封口，即得到可预锂化的锂离子启停电源。 Put the electrode group into an aluminum-plastic film packaging bag, use 1M LiPF 6 ethylene carbonate: ethyl methyl carbonate = 6:4 as the electrolyte, and complete the injection and one-time sealing under the condition of the dew point of -40°C. That is, a lithium ion start-stop power supply capable of pre-lithiation is obtained.
所制得的锂离子启停电源其首次效率为90％～92％，测试其倍率性能，电源在超大倍率，如40C倍率下，也可实现连续放电，放电容量可达初始容量的82.8％；通过测试该锂离子启停电源的低温性能，其在-20℃下，可实现大倍率放电，如在20C倍率放电下，容量可达初始容量的54.1％；对其500cy循环性能测定，可达到97.1％。The prepared lithium ion start-stop power supply has an initial efficiency of 90% to 92%. The rate performance is tested. The power supply can also achieve continuous discharge at a super-large rate, such as a 40C rate, and the discharge capacity can reach 82.8% of the initial capacity; By testing the low-temperature performance of the lithium-ion start-stop power supply, it can achieve high-rate discharge at -20°C. For example, under 20C rate discharge, the capacity can reach 54.1% of the initial capacity; its 500cy cycle performance can reach 97.1%.
实施例4Example 4
将Li 2O与Fe 2O 3按5:1的摩尔比机械混合后压制成片，并在 850℃下烧结20小时，得到Li 5FeO 4材料。之后，将LiNi 0.8Co 0.1Mn 0.1O 2(购自北京当升材料科技股份有限公司，中国)与得到的Li 5FeO 4材料，在干燥的环境中，按照质量比LiNi 0.8Co 0.1Mn 0.1O 2：Li 5FeO 4＝8：2的量混合后与氧化锆球按照球料重量比为60:1一同放入内衬为氧化锆材料的球磨罐内，在转速为500rmp/min的条件下干法球磨24h，之后过筛即得到LiNi 0.8Co 0.1Mn 0.1O 2Li 5FeO 4复合材料。 Li 2 O and Fe 2 O 3 were mechanically mixed at a molar ratio of 5:1 and then pressed into tablets, and sintered at 850° C. for 20 hours to obtain Li 5 FeO 4 materials. After that, LiNi 0.8 Co 0.1 Mn 0.1 O 2 (purchased from Beijing Dangsheng Material Technology Co., Ltd., China) and the obtained Li 5 FeO 4 material were combined in a dry environment according to the mass ratio of LiNi 0.8 Co 0.1 Mn 0.1 O 2 : Li 5 FeO 4 = 8:2, mixed with zirconia balls according to the ball weight ratio of 60:1, put them into a ball milling tank lined with zirconia material, at a speed of 500rmp/min Dry ball milling for 24 hours, then sieving to obtain LiNi 0.8 Co 0.1 Mn 0.1 O 2 Li 5 FeO 4 composite material.
将得到的LiNi 0.8Co 0.1Mn 0.1O 2/Li 5FeO 4复合材料、PVDF和炭黑按质量比92.5：2.5：5混合均匀后按固含量50％的量加入NMP溶剂搅拌3.5h，所得的浆料均匀涂覆于双面铝箔上成型，制备得复合材料电极，将复合电极材料经先烘干再碾压成片后切成带有极耳的正极片(5.9cm×10.9cm)成品若干。 The obtained LiNi 0.8 Co 0.1 Mn 0.1 O 2 /Li 5 FeO 4 composite material, PVDF and carbon black were mixed uniformly at a mass ratio of 92.5:2.5:5, and then NMP solvent was added at a solid content of 50% and stirred for 3.5 hours. The slurry is uniformly coated on double-sided aluminum foil to form a composite electrode. The composite electrode material is dried and then rolled into a sheet and then cut into a positive electrode sheet (5.9cm×10.9cm) with tabs (5.9cm×10.9cm). Several finished products .
将硬碳材料、羟甲基纤维素和丁苯橡胶、炭黑按质量比为93.5：2.5：4混合均匀后按固含量50％的量加入去离子水搅拌3.5h，所得的浆料均匀涂于双面铜箔上成型，制备得到碳电极，将碳电极经先烘干再碾压成片后切成带有极耳的负极片(6.0cm×11.0cm)成品若干。The hard carbon material, hydroxymethyl cellulose, styrene butadiene rubber, and carbon black are mixed uniformly in a mass ratio of 93.5:2.5:4, and then deionized water is added at a solid content of 50% and stirred for 3.5 hours. The resulting slurry is evenly coated Forming on double-sided copper foil to prepare a carbon electrode. The carbon electrode is dried and then rolled into a sheet, and then cut into a negative electrode sheet (6.0cm×11.0cm) with tabs (6.0cm×11.0cm).
将上述所制得的正负极电极片，以PP/PE复合微孔膜为隔膜，按照10片正极片、11片负极片进行叠片并联完成极耳焊接得到电极组。The positive and negative electrode sheets prepared above, using the PP/PE composite microporous membrane as the separator, are laminated in parallel according to 10 positive sheets and 11 negative sheets to complete the tab welding to obtain an electrode group.
将电极组放入铝塑膜包装袋中，以含1M的LiPF 6的碳酸乙烯酯:碳酸甲乙酯＝6:4为电解液，在露点-42.5℃的条件下完成注液以及一次封口，即得到可预锂化的锂离子启停电源。 Put the electrode group into an aluminum-plastic film packaging bag, use 1M LiPF 6 ethylene carbonate: ethyl methyl carbonate=6:4 as the electrolyte, and complete the injection and one-time sealing under the condition of the dew point -42.5℃. That is, a lithium ion start-stop power supply capable of pre-lithiation is obtained.
所制得的锂离子启停电源其首次效率为93％～94％，测试其倍率性能，电源在超大倍率，如40C倍率下，也可实现连续放电，放电容量可达初始容量的72.9％；通过测试该锂离子启停电源的低温性能，其在-20℃下，可实现大倍率放电，如在20C倍率放电下，容量可达初始容量的48.6％；对其500cy循环性能测定，可达到90.1％。The prepared lithium ion start-stop power supply has an initial efficiency of 93% to 94%. The rate performance is tested. The power supply can also achieve continuous discharge at a super-large rate, such as a 40C rate, and the discharge capacity can reach 72.9% of the initial capacity; By testing the low-temperature performance of the lithium-ion start-stop power supply, it can achieve high-rate discharge at -20°C. For example, under 20C rate discharge, the capacity can reach 48.6% of the initial capacity; its 500cy cycle performance can reach 90.1%.
对比实施例1Comparative Example 1
对比实施例1与实施例1的区别仅在于实施例1使用的是LiNi 0.6Co 0.2Mn 0.2O 2/Li 5FeO 4复合材料制得正极片，而对比实施例1使用的是实施例1中的LiNi 0.6Co 0.2Mn 0.2O 2制备方法得到的 LiNi 0.6Co 0.2Mn 0.2O 2制得正极片，其他步骤和条件均相同，在此不再详细赘述。通过对对比实施例1中得到的锂离子启停电源进行性能测试，可得其首次效率为75％，测试其倍率性能，电源在超大倍率，如40C倍率下，放电容量可达初始容量的65.2％；通过测试该锂离子启停电源的低温性能，其在-20℃下，如在20C倍率放电下，容量可达初始容量的42.5％；对其500cy循环性能测定，可达到89.5％。 The difference between Comparative Example 1 and Example 1 is only that Example 1 uses LiNi 0.6 Co 0.2 Mn 0.2 O 2 /Li 5 FeO 4 composite material to prepare the positive electrode sheet, while Comparative Example 1 uses the method in Example 1. The LiNi 0.6 Co 0.2 Mn 0.2 O 2 preparation method of LiNi 0.6 Co 0.2 Mn 0.2 O 2 is used to prepare a positive electrode sheet. The other steps and conditions are the same, and the details are not repeated here. Through the performance test of the lithium ion start-stop power supply obtained in Comparative Example 1, it can be obtained that its first efficiency is 75%, and its rate performance is tested. The discharge capacity of the power supply can reach 65.2 of the initial capacity at a super-large rate, such as a 40C rate. %; By testing the low temperature performance of the lithium ion start-stop power supply, its capacity can reach 42.5% of the initial capacity at -20°C, such as at 20C rate discharge; its 500cy cycle performance can reach 89.5%.
对比实施例2Comparative Example 2
对比实施例2与实施例2的区别仅在于实施例2使用的是LiNi 0.5Co 0.2Mn 0.3O 2/Li 5FeO 4复合材料制得正极片，而对比实施例2使用的是实施例2中的LiNi 0.5Co 0.2Mn 0.3O 2制备方法得到的LiNi 0.5Co 0.2Mn 0.3O 2制得正极片，其他步骤和条件均相同，在此不再详细赘述。通过对对比实施例2中得到的锂离子启停电源进行性能测试，可得其首次效率为72～73％，测试其倍率性能，电源在超大倍率，如40C倍率下，放电容量可达初始容量的63.4％；通过测试该锂离子启停电源的低温性能，其在-20℃下，如在20C倍率放电下，容量可达初始容量的41.7％；对其500cy循环性能测定，可达到88.7％。 The difference between Comparative Example 2 and Example 2 is only that Example 2 uses LiNi 0.5 Co 0.2 Mn 0.3 O 2 /Li 5 FeO 4 composite material to prepare the positive electrode sheet, while Comparative Example 2 uses the method in Example 2. The LiNi 0.5 Co 0.2 Mn 0.3 O 2 preparation method of LiNi 0.5 Co 0.2 Mn 0.3 O 2 is used to prepare a positive electrode sheet. The other steps and conditions are the same, and the details are not repeated here. Through the performance test of the lithium ion start-stop power supply obtained in Comparative Example 2, it can be obtained that its first efficiency is 72-73%, and its rate performance is tested. The discharge capacity of the power supply can reach the initial capacity at a super-large rate, such as a 40C rate. By testing the low temperature performance of the lithium-ion start-stop power supply, its capacity can reach 41.7% of the initial capacity at -20℃, such as at 20C rate discharge; its 500cy cycle performance measurement can reach 88.7% .
对比实施例3Comparative Example 3
对比实施例3与实施例3的区别仅在于实施例3使用的是LiNi 1/3Co 1/3Mn 1/3O 2/Li 5FeO 4复合材料制得正极片，而对比实施例3使用的是实施例3中的LiNi 1/3Co 1/3Mn 1/3O 2制备方法得到的LiNi 1/3Co 1/3Mn 1/3O 2制得正极片，其他步骤和条件均相同，在此不再详细赘述。通过对对比实施例3中得到的锂离子启停电源进行性能测试，可得其首次效率为75～76％，测试其倍率性能，电源在超大倍率，如40C倍率下，放电容量可达初始容量的69.4％；通过测试该锂离子启停电源的低温性能，其在-20℃下，如在20C倍率放电下，容量可达初始容量的44.3％；对其500cy循环性能测定，可达到89.5％。 The difference between Comparative Example 3 and Example 3 is only that Example 3 uses LiNi 1/3 Co 1/3 Mn 1/3 O 2 /Li 5 FeO 4 composite material to make the positive electrode sheet, while Comparative Example 3 uses that LiNi 1/3 Co 1/3 Mn 1/3 O 2 positive electrode sheet prepared in Example 3 LiNi 1/3 Co 1/3 Mn 1/3 O 2 preparation obtained, the other steps and conditions are the same , I won’t go into details here. Through the performance test of the lithium ion start-stop power supply obtained in Comparative Example 3, it can be obtained that its first efficiency is 75-76%, and its rate performance is tested. The discharge capacity of the power supply can reach the initial capacity at a super-large rate, such as a 40C rate. By testing the low-temperature performance of the lithium-ion start-stop power supply, its capacity can reach 44.3% of the initial capacity at -20°C, such as at 20C rate discharge; its 500cy cycle performance measurement can reach 89.5% .
对比实施例4Comparative Example 4
对比实施例4与实施例4的区别仅在于实施例4使用的是LiNi 0.8Co 0.1Mn 0.1O 2/Li 5FeO 4复合材料制得正极片，而对比实施例4使 用的是实施例4中的LiNi 0.8Co 0.1Mn 0.1O 2制备方法得到的LiNi 0.8Co 0.1Mn 0.1O 2制得正极片，其他步骤和条件均相同，在此不再详细赘述。通过对对比实施例4中得到的锂离子启停电源进行性能测试，可得其首次效率为71～72％，测试其倍率性能，电源在40C倍率下，放电容量可达初始容量的63.4％；通过测试该锂离子启停电源的低温性能，其在-20℃下，如在20C倍率放电下，容量可达初始容量的39.5％；对其500cy循环性能测定，可达到85.2％。 The difference between Comparative Example 4 and Example 4 is that Example 4 uses LiNi 0.8 Co 0.1 Mn 0.1 O 2 /Li 5 FeO 4 composite material to prepare the positive electrode sheet, while Comparative Example 4 uses the method in Example 4. The LiNi 0.8 Co 0.1 Mn 0.1 O 2 preparation method of LiNi 0.8 Co 0.1 Mn 0.1 O 2 is used to prepare a positive electrode sheet. The other steps and conditions are the same, and the details are not repeated here. Through the performance test of the lithium ion start-stop power supply obtained in Comparative Example 4, it can be obtained that its first efficiency is 71-72%, and its rate performance is tested, and the discharge capacity of the power supply can reach 63.4% of the initial capacity at a rate of 40C; By testing the low-temperature performance of the lithium ion start-stop power supply, its capacity can reach 39.5% of the initial capacity at -20°C, such as under 20C rate discharge; its 500cy cycle performance can reach 85.2%.
将上述实施例中得到的锂离子启停电源性能检测数据通过表格显示进行比对，具体请见表1。The lithium ion start-stop power supply performance test data obtained in the above examples are compared through the table display, see Table 1 for details.
表1Table 1
Figure PCTCN2020079786-appb-000001
Figure PCTCN2020079786-appb-000001
通过对实施例1～4和对比实施例1～4中得到的锂离子启停电源性能检测数据进行比较，可以看出，根据本发明的方法得到的可预锂化的锂离子启停电源不论在首次效率、功率还是在低温性能上都比对比实施例中的锂离子启停电源性能优越，因此本发明的锂离子启停电源具有广泛的应用前景。By comparing the performance detection data of lithium ion start-stop power supply obtained in Examples 1 to 4 and Comparative Examples 1 to 4, it can be seen that the pre-lithiated lithium ion start-stop power supply obtained according to the method of the present invention does not matter The performance of the lithium-ion start-stop power supply in the comparative example is superior in terms of first efficiency, power, and low-temperature performance. Therefore, the lithium-ion start-stop power supply of the present invention has a wide range of application prospects.
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明披露的技术范围内，可轻易想到的变化或替换，都应该涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求书的保护范围为准。The above are only preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or changes within the technical scope disclosed in the present invention. All replacements should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims (15)

  1. 一种可预锂化的锂离子启停电源，包括正极和负极，其特征在于：所述正极主要由LiNi xCo yMn zO 2/Li 5FeO 4复合材料制成，其中x+y+z＝1。 A pre-lithiated lithium ion start-stop power supply, comprising a positive electrode and a negative electrode, characterized in that: the positive electrode is mainly made of LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material, wherein x+y+ z=1.
  2. 根据权利要求1所述的启停电源，其特征在于：所述Li 5FeO 4是通过将Li 2O与Fe 2O 3按摩尔比为5:1的量机械混合，压制成片，最后在高温下烧结而制成。 The start-stop power supply according to claim 1, wherein the Li 5 FeO 4 is mechanically mixed with a molar ratio of Li 2 O and Fe 2 O 3 at a molar ratio of 5:1, compressed into tablets, and finally It is made by sintering at high temperature.
  3. 根据权利要求1所述的启停电源，其特征在于：所述LiNi xCo yMn zO 2/Li 5FeO 4复合材料是通过将LiNi xCo yMn zO 2和Li 5FeO 4按质量比为(0.8～0.98):(0.02～0.2)的量混合后经球磨而制成。 The start-stop power supply according to claim 1, characterized in that: the LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material is made by combining LiNi x Co y Mn z O 2 and Li 5 FeO 4 by mass The ratio is (0.8～0.98):(0.02～0.2), mixed and ball milled to make it.
  4. 根据权利要求1所述的启停电源，其特征在于：所述LiNi xCo yMn zO 2选自LiNi 1/3Co 1/3Mn 1/3O 2、LiNi 0.5Co 0.2Mn 0.3O 2、LiNi 0.6Co 0.2Mn 0.2O 2、LiNi 0.8Co 0.1Mn 0.1O 2中的一种或多种。 The start-stop power supply according to claim 1, wherein the LiNi x Co y Mn z O 2 is selected from LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 One or more of LiNi 0.6 Co 0.2 Mn 0.2 O 2 and LiNi 0.8 Co 0.1 Mn 0.1 O 2.
  5. 一种制备权利要求1～4任一项所述的可预锂化的锂离子启停电源的方法，其特征在于，该方法包括以下步骤：A method for preparing the pre-lithiated lithium ion start-stop power supply according to any one of claims 1 to 4, characterized in that the method comprises the following steps:
    (1)制备LiNi xCo yMn zO 2/Li 5FeO 4复合材料； (1) Preparation of LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material;
    (2)将得到的LiNi xCo yMn zO 2/Li 5FeO 4复合材料、粘结剂、导电剂混合均匀后加入溶剂搅拌2～5h，得到的浆料涂覆于铝箔上成型，制备得复合材料电极，将复合电极材料经先烘干再碾压成片后切成带有极耳的正极片成品； (2) Mix the obtained LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material, binder, and conductive agent uniformly, add the solvent and stir for 2 to 5 hours, and coat the obtained slurry on aluminum foil for forming. To obtain a composite electrode, the composite electrode material is dried and then rolled into a sheet, and then cut into a positive electrode sheet with tabs;
    (3)将石墨或硬碳、粘结剂、导电剂混合均匀后加入溶剂搅拌2～5h，得到的浆料涂覆于铜箔上成型，制备得到碳电极，将碳电极经先烘干再碾压成片后切成带有极耳的负极片成品；(3) Mix the graphite or hard carbon, the binder, and the conductive agent evenly, then add the solvent and stir for 2 to 5 hours, and the slurry obtained is coated on the copper foil to form a carbon electrode. The carbon electrode is dried and then After rolling into pieces, cut into finished negative pieces with tabs;
    (4)分别将步骤(2)和(3)得到的电极片成品作为正负极，以PP/PE复合微孔膜为隔膜，进行叠片并联完成极耳的焊接得到电极组；(4) The finished electrode sheets obtained in steps (2) and (3) are used as positive and negative electrodes, and the PP/PE composite microporous membrane is used as the diaphragm, and the electrodes are stacked in parallel to complete the welding of the tabs to obtain an electrode group;
    (5)将电极组放入铝塑膜包装袋中，以含1M的LiPF 6的碳酸乙烯酯：碳酸甲乙酯＝6:4为电解液，在露点-45℃～-40℃的条件下完成注液及一次封口，即得到锂离子启停电源。 (5) Put the electrode group into an aluminum-plastic film packaging bag, use 1M LiPF 6 ethylene carbonate: ethyl methyl carbonate = 6:4 as the electrolyte, and under the condition of dew point -45℃～-40℃ After the liquid injection and one-time sealing are completed, the lithium ion start-stop power supply is obtained.
  6. 根据权利要求5所述的方法，其特征在于：所述步骤(1)中，所述LiNi xCo yMn zO 2/Li 5FeO 4复合材料是由以下步骤制备而成： The method according to claim 5, wherein in the step (1), the LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material is prepared by the following steps:
    a.将Li 2O和Fe 2O 3混合后压制成片并在700～900℃的条件下烧结15～25h得到Li 5FeO 4材料。 a. After mixing Li 2 O and Fe 2 O 3, they are pressed into tablets and sintered at 700-900° C. for 15-25 hours to obtain Li 5 FeO 4 materials.
    b.将得到的Li 5FeO 4和LiNi xCo yMn zO 2混合后进行球磨，之后过筛即得到LiNi xCo yMn zO 2/Li 5FeO 4复合材料。 b. The obtained Li 5 FeO 4 and LiNi x Co y Mn z O 2 are mixed and ball milled, and then sieved to obtain a LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material.
  7. 根据权利要求5所述的方法，其特征在于：所述步骤a中，所述Li 2O和Fe 2O 3的摩尔比为5:1。 The method according to claim 5, characterized in that: in the step a, the molar ratio of Li 2 O to Fe 2 O 3 is 5:1.
  8. 根据权利要求5所述的方法，其特征在于：所述步骤b中，所述LiNi xCo yMn zO 2和Li 5FeO 4的质量比为(0.8～0.98):(0.02～0.2)。 The method according to claim 5, characterized in that: in the step b, the mass ratio of the LiNi x Co y Mn z O 2 and Li 5 FeO 4 is (0.8 to 0.98): (0.02 to 0.2).
  9. 根据权利要求8所述的方法，其特征在于：所述LiNi xCo yMn zO 2满足x+y+z＝1，可选自LiNi 1/3Co 1/3Mn 1/3O 2、LiNi 0.5Co 0.2Mn 0.3O 2、LiNi 0.6Co 0.2Mn 0.2O 2、LiNi 0.8Co 0.1Mn 0.1O 2中的一种或多种。 The method according to claim 8, wherein the LiNi x Co y Mn z O 2 satisfies x+y+z=1, and can be selected from LiNi 1/3 Co 1/3 Mn 1/3 O 2 , One or more of LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiNi 0.6 Co 0.2 Mn 0.2 O 2 , and LiNi 0.8 Co 0.1 Mn 0.1 O 2 .
  10. 根据权利要求5所述的方法，其特征在于：所述步骤b中，所述LiNi xCo yMn zO 2/Li 5FeO 4复合材料是通过将Li 5FeO 4和LiNi xCo yMn zO 2混合后放入内衬为氧化锆材料的球磨罐中，以高纯氧化锆球为球磨介质，按照球料重量比为60:1，在转速为300～600rmp/min的条件下球磨2～24h后过筛而得到的。 The method according to claim 5, characterized in that: in the step b, the LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material is obtained by combining Li 5 FeO 4 and LiNi x Co y Mn z After O 2 is mixed, put it into a ball milling tank lined with zirconia material, use high-purity zirconia balls as the ball milling medium, according to the weight ratio of the ball to 60:1, and ball mill 2 under the condition of 300～600rmp/min. Obtained by sieving after ~24h.
  11. 根据权利要求5所述的方法，其特征在于：所述步骤(2)中，所述LiNi xCo yMn zO 2/Li 5FeO 4复合材料、粘结剂、导电剂的质量比为(80～98):(1～5):(0.5～10)。 The method according to claim 5, characterized in that: in the step (2), the mass ratio of the LiNi x Co y Mn z O 2 /Li 5 FeO 4 composite material, the binder, and the conductive agent is ( 80～98):(1～5):(0.5～10).
  12. 根据权利要求5或11所述的方法，其特征在于：所述步骤(2)中，所述粘结剂为质量分数为2％～10％的PVDF溶液；所述溶剂为NMP溶液，其按固含量40％～70％的量加入。The method according to claim 5 or 11, characterized in that: in the step (2), the binder is a PVDF solution with a mass fraction of 2% to 10%; the solvent is an NMP solution, which is The solid content is added in an amount of 40% to 70%.
  13. 根据权利要求5所述的方法，其特征在于：所述步骤(3)中，所述石墨或硬碳、粘结剂、导电剂的质量比为(80～98):(1～5):(0.5～8)。The method according to claim 5, characterized in that: in the step (3), the mass ratio of the graphite or hard carbon, the binder, and the conductive agent is (80~98):(1~5): (0.5～8).
  14. 根据权利要求5或13所述的方法，其特征在于：所述步骤(3)中，所述粘结剂为丙烯腈多元共聚物、羟甲基纤维素、丁苯橡胶中的一种或多种；所述溶剂为水，其按固含量40％～70％的量加入。The method according to claim 5 or 13, characterized in that: in the step (3), the binder is one or more of acrylonitrile multi-element copolymer, hydroxymethyl cellulose, and styrene butadiene rubber. Species; the solvent is water, which is added in an amount of 40% to 70% of the solid content.
  15. 根据权利要求5所述的方法，其特征在于：所述导电剂选自炭黑、导电石墨、碳纤维、碳纳米管中的一种或多种。The method according to claim 5, wherein the conductive agent is selected from one or more of carbon black, conductive graphite, carbon fiber, and carbon nanotube.
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