CN105932334A - High-energy lithium ion battery and fabrication method thereof - Google Patents

High-energy lithium ion battery and fabrication method thereof Download PDF

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CN105932334A
CN105932334A CN201610283425.7A CN201610283425A CN105932334A CN 105932334 A CN105932334 A CN 105932334A CN 201610283425 A CN201610283425 A CN 201610283425A CN 105932334 A CN105932334 A CN 105932334A
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lithium ion
ion battery
lithium
step
positive electrode
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刘立君
宋翠环
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深圳市力为锂能科技有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/058Construction or manufacture
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381Alkaline or alkaline earth metals elements
    • H01M4/382Lithium
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/12Battery technologies with an indirect contribution to GHG emissions mitigation
    • Y02E60/122Lithium-ion batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/60Other road transportation technologies with climate change mitigation effect
    • Y02T10/70Energy storage for electromobility
    • Y02T10/7005Batteries
    • Y02T10/7011Lithium ion battery

Abstract

The invention discloses a high-energy lithium ion battery and a fabrication method thereof. By coating the surface of lithium metal with a nanometer lithium fast ion conductor ceramic layer, side reaction between the lithium metal and an electrolyte during charging and discharging is prevented, metallic lithium dendrite is also prevented from forming and growing, meanwhile, the resistance of a protection film to lithium ion migration is reduced, the impedance increase of the protection film on the battery is substantially reduced, so that high-energy density output can be achieved while the cycle safety of the battery is ensured and the service lifetime of the battery is prolonged, and the energy demand of electric vehicle driving range is met.

Description

一种高能量锂离子电池及其制备方法 A high-energy lithium ion battery and its preparation method

技术领域 FIELD

[0001]本发明涉及锂离子电池领域,尤其涉及一种高能量锂离子电池及其制备方法。 [0001] The present invention relates to a lithium ion battery, and more particularly relates to a high-energy lithium ion battery and its preparation method.

背景技术 Background technique

[0002]随着科技进步,各种电器的小型化、超薄化发展趋势需要,人们迫切需要一种高能量密度电池。 [0002] As technology advances, miniaturization of various appliances, ultra-thin trends needs, there is an urgent need for a high energy density batteries. 常规锂离子电池的负极使用石墨为负极,石墨不仅理论容量低(只有372mAh/g),而且首次不可逆容量损失大,无法成为高能量密度电池。 Conventional lithium-ion battery anode using graphite as the anode, the theoretical capacity of graphite is not only low (only 372mAh / g), and the first large irreversible capacity loss, can not become a high-energy density batteries. 而金属锂的理论容量达3860mAh/g,且锂电极的交换电流密度大、极化小,是理想的电池材料。 The theoretical capacity of lithium metal was 3860mAh / g, the lithium electrode and the exchange current density, a small polarization, is an ideal battery material. 但锂电极的实际应用中还存在一些需要解决的问题,枝晶问题以及与电解液的相容性问题。 But the practical application of the lithium electrode there are still some problems to be solved, dendrite issues and compatibility problems with the electrolyte.

[0003]金属锂与普通电解液的反应活性高,往往在锂负极表面形成针状枝晶,如果枝晶过度生长并与正极接触,则会发生内部短路,引发安全问题,严重影响了金属锂电池的循环寿命,抑制了高能量密度金属锂电池的实际应用。 [0003] The high reactivity of metallic lithium with an ordinary electrolytic solution tends to form acicular dendrites of lithium negative electrode surface, and if dendrite overgrowth in contact with the positive electrode, an internal short circuit occurs, causing security problems, a serious impact on metal lithium the cycle life of the battery, suppressing the practical application of high energy density lithium-metal batteries. 为了使高能量密度金属锂电池得到理想的循环寿命,必须降低金属锂与电解液的反应活性,但又不能彻底钝化金属锂,致使不能实现高的放电电流密度。 In order to obtain a high energy density lithium-metal batteries over the cycle life of metallic lithium is necessary to reduce the reactivity with the electrolytic solution, but not fully passivated lithium metal, making it impossible to realize a high discharge current density.

[0004]对于金属锂负极的改性中也有涉及表面涂覆保护层的实例,但多为没有锂离子导电性的保护层,虽然改善了金属锂负极的表面形貌,但极大的增大了电池内部阻抗,影响了电池性能发挥,限制了金属锂负极在锂离子电池中的实际应用。 [0004] For the negative electrode of metal lithium but also in the modified example relates to a surface coated with a protective layer, but mostly no lithium ion conductive protective layer, although improving the surface morphology of the lithium metal anode, but greatly increased internal impedance of the battery, the battery performance affect play, limiting the practical applicability of metallic lithium in the negative electrode of a lithium ion battery.

[0005]因此,现有技术还有待于改进和发展。 [0005] Thus, the prior art has yet to be improved and developed.

发明内容 SUMMARY

[0006]鉴于上述现有技术的不足,本发明的目的在于提供一种锂离子电池及其制备方法,旨在解决现有锂离子电池仍然难以满足实际需要、电池内部阻抗大和循环寿命短的问题。 [0006] In view of the deficiencies of the prior art, an object of the present invention to provide a lithium ion battery and its preparation method, to solve the conventional lithium-ion battery is still difficult to meet the actual needs, the internal battery impedance short cycle life problems Japan .

[0007]本发明的技术方案如下: [0007] aspect of the present invention is as follows:

一种高能量锂离子电池的制备方法,其中,包括步骤: Method for preparing a high-energy lithium ion battery, comprising the steps of:

A、将纳米锂快离子导体陶瓷粉、粘接剂按照85〜90:10〜15质量比例加入到有机溶剂中充分混合均匀成负极浆料,将负极浆料于惰性气氛中涂于锂箔上,烘干后、碾压得表面覆有纳米锂快离子导体陶瓷层的负极极片; A, fast ion conductor nano ceramic powder adhesive according 85~90: 10 ~ 15 by mass ratio was added to the organic solvent sufficiently mixing a negative electrode slurry, the slurry was applied to negative electrode of lithium foil in an inert atmosphere after drying, the surface is coated with nano-rolling to obtain fast ion conductive ceramic sheet negative electrode layer;

B、将正极材料、导电剂、粘结剂按照80〜85:5〜10:7〜12的质量比例加入到溶剂中充分混合均匀成正极浆料,将正极浆料涂于铝箔上,烘干后、碾压得正极极片; B, and a positive electrode material, a conductive agent, a binder according to 80~85: 7~12 added mass ratio of the solvent to sufficiently mixing a positive electrode slurry, the positive electrode slurry was applied on an aluminum foil, drying: 5 to 10 after rolling to obtain positive electrode tab;

C、将正极、负极极片按照不同的电芯设计裁剪成相应尺寸,真空干燥除去溶剂和水分,备用; C, the positive electrode, the negative electrode cut to a different cell according to the corresponding dimension of the pole piece design, the solvent was removed in vacuo and water and dried for later use;

D、将备用的正极、负极极片、隔膜和电解液组装锂离子电池,静置8〜1h; D, and alternate positive electrode, a negative electrode plate, a separator and an electrolyte assembly of a lithium ion battery, standing 8~1h;

E、对锂离子电池进行化成,所述化成工步为0.0lO0.03C小电流充电至3.2-3.6V, E, into lithium ion batteries, the chemical conversion process step of charging current to 0.0lO0.03C 3.2-3.6V,

0.0500.IC充至3.8〜4.0V,以0.卜0.3C放电至2.8-3.2V,充放循环2〜4次; 0.0500.IC charged to 3.8~4.0V, 0.5 to 0.3C discharge to BU 2.8-3.2V, 2 ~ 4 times charge-discharge cycle;

F、对化成好的锂离子电池静置5〜9天,进行容量、倍率、循环寿命测试,电压测试范围3.0V-4.2Vo F., For a lithium ion battery into good standing 5~9 days, the capacity, rate, cycle life test, the test voltage range of 3.0V-4.2Vo

[0008]所述的高能量锂离子电池的制备方法,其中,步骤A中,所述纳米锂快离子导体陶瓷粉为LiiQGeP2S12、Li3N、LaQ.5Li().5Ti03 Ji7P3S11^i1QSnPShLi11Si2PS12 中的一种。 Preparation [0008] The method of the high-energy lithium ion battery, wherein, in step A, the fast ion conductor lithium nano ceramic powder is LiiQGeP2S12, Li3N, LaQ.5Li (). 5Ti03 Ji7P3S11 ^ i1QSnPShLi11Si2PS12 of one.

[0009]所述的高能量锂离子电池的制备方法,其中,步骤A中,所述纳米锂快离子导体陶瓷粉颗粒粒度为10-200nm。 [0009] The method of preparing a high energy lithium ion battery, wherein, in step A, the fast ion conductor lithium nano ceramic powder particle size of 10-200nm.

[0010]所述的高能量锂离子电池的制备方法,其中,步骤A中,负极极片表面的纳米锂快离子导体陶瓷层厚度为1〜10μπι。 Preparation [0010] The method of the high-energy lithium ion battery, wherein, in step A, the negative electrode of lithium nano-ceramic fast ion conductor layer is the thickness of the electrode substrate surface 1~10μπι.

[0011 ]所述的高能量锂离子电池的制备方法,其中,步骤B中,将正极材料、导电剂、粘结剂按照82:8:10的质量比例加入到溶剂中。 [0011] The method of preparing a high energy lithium ion battery, wherein, in step B, the positive electrode material, a conductive agent, a binder 82 according to: the mass added to the solvent of Comparative Example 10: 8.

[0012]所述的高能量锂离子电池的制备方法,其中,步骤B中,所述溶剂为NMP溶剂。 Preparation [0012] The method of the high-energy lithium ion battery, wherein, in step B, the solvent is NMP solvent.

[0013] 所述的高能量锂离子电池的制备方法,其中,步骤D中,所述隔膜为Celgard 2400。 Preparation [0013] The method of the high-energy lithium ion battery, wherein, in step D, the separator is Celgard 2400.

[0014]所述的高能量锂离子电池的制备方法,其中,步骤D中,所述电解液为LiPF6/EC-EMC-DMC、LiAsF6/PC-EMC-DMC、LiBF4/MPC-EMC-DMC 中的一种。 [0014] The method of preparing a high energy lithium ion battery, wherein, in step D, the electrolyte is LiPF6 / EC-EMC-DMC, LiAsF6 / PC-EMC-DMC, LiBF4 / MPC-EMC-DMC in a.

[0015]所述的高能量锂离子电池的制备方法,其中,步骤E中,所述化成工步为0.02C小电流充电至3.4V,0.1C充至3.0V。 [0015] The method of preparing the high-energy lithium ion battery, wherein, in step E, into the process step of 0.02C charging current to 3.4V, 0.1C charge to 3.0V.

[0016] —种高能量锂离子电池,其中,采用如上任一所述的高能量锂离子电池的制备方法制备而成。 [0016] - Type High-energy lithium ion batteries, which were prepared as a preparation method of the incoming high energy lithium ion batteries made.

[0017]有益效果:本发明将纳米锂快离子导体陶瓷粉涂覆、粘接在金属锂表面,形成纳米锂快离子导体陶瓷层,抑制了金属锂和电解液之间的非法拉第反应,从而提高金属锂的耐腐蚀性能;同时纳米锂快离子导体陶瓷层减少了锂离子迀移的阻力,减少了电池充放过程中的极化阻抗。 [0017] Advantageous Effects: The present invention is a lithium fast ion conductor nano ceramic powder coated on the adhesive surface of metal lithium, lithium fast ion conductor forming a nano ceramic layer suppresses a reaction between the metal lithium nonfaradiac and an electrolyte, whereby to improve the corrosion resistance of metal lithium; fast ion conductor while nano-ceramic layer reduces the resistance of the lithium ions move Gan, reducing the polarization impedance of the battery charging and discharging process.

具体实施方式 Detailed ways

[0018]本发明提供一种高能量锂离子电池及其制备方法,为使本发明的目的、技术方案及效果更加清楚、明确,以下对本发明进一步详细说明。 [0018] The present invention provides a high-energy lithium ion battery and its preparation method, for the purposes of the present invention, technical solutions and advantages clearer, explicit, the following detailed description of the present invention further. 应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。 It should be understood that the specific embodiments described herein are only intended to illustrate the present invention and are not intended to limit the present invention.

[0019]本发明的一种高能量锂离子电池的制备方法,其中,包括步骤: [0019] The method for producing a high-energy lithium ion battery according to the present invention, comprising the steps of:

A、将纳米锂快离子导体陶瓷粉、粘接剂按照85〜90:10〜15质量比例加入到有机溶剂中充分混合均匀成负极浆料,将负极浆料于惰性气氛中涂于锂箔上,烘干后、碾压得表面覆有纳米锂快离子导体陶瓷层的负极极片; A, fast ion conductor nano ceramic powder adhesive according 85~90: 10 ~ 15 by mass ratio was added to the organic solvent sufficiently mixing a negative electrode slurry, the slurry was applied to negative electrode of lithium foil in an inert atmosphere after drying, the surface is coated with nano-rolling to obtain fast ion conductive ceramic sheet negative electrode layer;

所述步骤A中,通过在金属锂负极表面涂覆一层纳米锂快离子导体陶瓷层,使得金属锂负极可在常规电解液环境下安全、高效的发挥作用。 Said step A, the negative electrode surface is coated by a layer of nano lithium fast ion conductor layer on the ceramic metal lithium, metal lithium negative electrode that can be safe and effective role in the electrolytic solution under conventional conditions. 优选地,本发明所述纳米锂快离子导体陶瓷粉可以为LiiQGeP2S12、Li3N、LaQ.5Li().5Ti03 Ji7P3S11^i1QSnPShLi11Si2PS12 中的一种。 Preferably, the present invention is the nano ceramic powder fast ion conductors may be LiiQGeP2S12, Li3N, LaQ.5Li (). 5Ti03 Ji7P3S11 ^ i1QSnPShLi11Si2PS12 of one kind.

[0020] 优选地,所述纳米锂快离子导体陶瓷粉颗粒粒度为10〜200nm。 [0020] Preferably, the nano-fast ion conductor ceramic powder particle size of 10~200nm. 更优选地,所述纳米锂快离子导体陶瓷粉颗粒粒度为20〜50nm。 More preferably, the nano-fast ion conductor is a ceramic powder particle size 20~50nm.

[0021]优选地,负极极片表面的纳米锂快离子导体陶瓷层厚度为I〜ΙΟμπι。 [0021] Preferably, the lithium negative electrode nano ceramic fast ion conductor layer is the thickness of the sheet surface electrode I~ΙΟμπι. 更优选地,负极极片表面的纳米锂快离子导体陶瓷层厚度为2〜6μπι。 More preferably, the lithium negative electrode nano ceramic fast ion conductor layer is the thickness of the sheet surface electrode 2~6μπι.

[0022] B、将正极材料、导电剂、粘结剂按照80〜85:5〜10:7〜12的质量比例加入到溶剂中充分混合均匀成正极浆料,将正极浆料涂于铝箔上,烘干后、碾压得正极极片; 优选地,将正极材料、导电剂、粘结剂按照82:8:10的质量比例加入到溶剂中。 [0022] B, a positive electrode material, a conductive agent, a binder according to 80~85: 5 to 10: 7~12 were added to the mass ratio of the solvent to fully mixed into the positive electrode slurry, the positive electrode slurry was applied on an aluminum foil after drying, rolling to obtain positive electrode sheets; preferably, the positive electrode material, a conductive agent, a binder 82 according to: the mass added to the solvent of Comparative Example 10: 8. 其中,所述溶剂为N-甲基吡咯烷酮(NMP )。 Wherein said solvent is N- methylpyrrolidone (NMP).

[0023] C、将正极、负极极片按照不同的电芯设计裁剪成相应尺寸,真空干燥除去溶剂和水分,备用; [0023] C, the positive electrode, the negative electrode cut to a different cell according to the corresponding dimension of the pole piece design, the solvent was removed in vacuo and water and dried for later use;

D、将备用的正极、负极极片、隔膜和电解液组装锂离子电池,静置8〜1h; D, and alternate positive electrode, a negative electrode plate, a separator and an electrolyte assembly of a lithium ion battery, standing 8~1h;

优选地,步骤D中,所述隔膜为Celgard 2400。 Preferably, step D, the separator is Celgard 2400. 所述电解液为LiPF6/EC-EMC_DMC、LiAsF6/PC-EMC-DMC、LiBF4/MPC-EMC-DMC 中的一种。 The electrolyte is LiPF6 EC-EMC_DMC, LiAsF6 / PC-EMC-DMC, LiBF4 / MPC-EMC-DMC in a /.

[0024] E、对锂离子电池进行化成,所述化成工步为0.0lO0.03C小电流充电至3.2-3.6V,0.05 00.1C充至3.8〜4.0V,以0.I〜0.3C放电至2.8-3.2V,充放循环2~4次; [0024] E, into lithium ion batteries, the chemical conversion process step of charging current to 0.0lO0.03C 3.2-3.6V, 0.05 00.1C charge to 3.8~4.0V, in order to discharge 0.I~0.3C 2.8-3.2V, charge-discharge cycle 2 to 4 times;

优选地,步骤E中,所述化成工步为0.02C小电流充电至3.4V,0.1C充至3.0V。 Preferably, in step E, into the process step of 0.02C charging current to 3.4V, 0.1C charge to 3.0V.

[0025] F、对化成好的锂离子电池静置5〜9天,进行容量、倍率、循环寿命测试,电压测试范围3.0V-4.2V。 [0025] F, for a lithium ion battery into good standing 5~9 days, the capacity, rate, cycle life test, the test voltage range of 3.0V-4.2V.

[0026]本发明通过在金属锂表面涂覆了一层纳米锂快离子导体陶瓷层,不仅阻止了金属锂与电解液在充放电期间的副反应,而且抑制了金属锂枝晶的形成与生长,同时减小了保护膜对锂离子迀移的阻力,大幅减缓保护膜对电池阻抗的增加,从而能在保证了电池的循环安全性、提高电池使用寿命的同时,实现高能量密度输出,满足电动车续航里程的能量需求。 [0026] In the present invention, by coating the surface of the metal lithium fast ion conductor layer of nano ceramic layers of lithium, lithium metal not only prevents the side reaction with the electrolyte during charging and discharging, but also inhibits the formation and growth of metal lithium dendrite while reducing protective film of lithium ions move Gan resistance, significant reduction of the protective film to increase the impedance of the battery, which can ensure the safety of the battery cycle, while improving battery life, high energy density output to meet the energy requirements of the electric vehicle mileage.

[0027]本发明还提供一种高能量锂离子电池,其中,采用如上任一所述的高能量锂离子电池的制备方法制备而成。 [0027] The present invention further provides a high-energy lithium ion batteries, which were prepared as a preparation method of the incoming high energy lithium ion batteries made. 本发明锂离子电池不仅具有高的电池循环安全性和电池使用寿命,同时具有高的电池能量密度,满足电动车续航里程的能量需求。 The present invention is not only the lithium ion battery having high safety of battery cycle life and battery, and a battery having a high energy density to meet the energy requirements of an electric vehicle mileage.

[0028]下面通过具体的实施例对本发明进行详细说明。 [0028] The following detailed description of the embodiments of the present invention through specific embodiments.

[0029] 实施例1 [0029] Example 1

将050为0.19711的纳米锂快离子导体陶瓷粉1^必、粘结剂按照90:10质量比例,分别称取,加入到有机溶剂NMP中充分混合均匀成负极浆料,将成负极浆料于惰性气氛他中涂于锂箔上,挥发掉溶剂,碾压后得表面覆有纳米锂快离子导体陶瓷层的金属锂负极;将正极材料磷酸铁锂、导电剂、粘结剂按照82:8:10的质量比例加入到匪P溶剂中充分混合均匀成正极浆料,将正极浆料涂于铝箔上,烘干、碾压后得正极极片;将正极、负极极片按照不同的电芯设计裁剪成相应尺寸,本实施例1电芯尺寸设计为8(T)X34(W)X50(H)mm<a20°C真空干燥除去溶剂和水分,备用;以Celgard 2400为隔膜,lmol/L的LiPF6/EC-EMC_DMC(体积比为1:1:1)为电解液,组装锂离子电池,静置8h。 The 050 0.19711 fast ion conductor nano ceramic powder 1 ^ will binder mass ratio of 90:10, respectively, weighed, added to the organic solvent in NMP fully mixed into a negative electrode paste, negative electrode paste in an inert become he applied to the upper atmosphere, a lithium foil, evaporate the solvent, to obtain the rolling surface of lithium metal anode coated with lithium nano-ceramic fast ion conductor layer; lithium iron phosphate positive electrode material, a conductive agent, a binder in accordance with 82: 8: mass ratio of 10 was added to the mixed solvent bandit P uniformly positive electrode paste, the positive electrode slurry was applied on an aluminum foil, drying, rolling to obtain positive electrode sheets; positive electrode, negative electrode sheet in a different cell design cut to the appropriate size, the present embodiment 1 cell size embodiment is designed to 8 (T) X34 (W) X50 (H) mm <a20 ° C vacuum drying to remove the solvent and water, standby; in Celgard 2400 as the membrane, lmol / L of LiPF6 / EC-EMC_DMC (volume ratio of 1: 1: 1) as the electrolyte, a lithium ion battery is assembled, left 8h.

[0030] 对电池进行化成,所述的化成工步为0.02C小电流充电至3.4V,0.08C充至4.0V,以 [0030] into the battery, the chemical conversion process step of 0.02C charging current to 3.4V, 0.08C charged to 4.0V, to

0.1C放电至3.0V,充放循环3次;对化成好的电池静置7天,进行容量、倍率、循环寿命测试,电压测试范围3.0V-4.2V。 0.1C discharge to 3.0V, 3 cycles of charge and discharge; good chemical conversion of the battery was allowed to stand for 7 days the capacity, rate, cycle life test, the test voltage range of 3.0V-4.2V.

[0031 ] 测试结果:5C充放,电池容量为145mAh/g ;循环500次,容量保持率为83%。 [0031] Test Results: 5C charge and discharge, the battery capacity was 145mAh / g; 500 cycles, the capacity retention rate was 83%.

[0032] 实施例2 [0032] Example 2

将D50为0.103μ的纳米锂快离子导体陶瓷粉Li1OGeP2S12、粘结剂按照85:15质量比例,分别称取,加入到有机溶剂NMP中充分混合均匀成负极浆料,将负极浆料于惰性气氛中涂于锂箔上,挥发掉溶剂,碾压后得表面覆有纳米锂快离子导体陶瓷层的金属锂负极;将正极材料磷酸铁锂、导电剂、粘结剂按照82:8:10的质量比例加入到NMP溶剂中充分混合均匀成正极浆料,将正极浆料涂于铝箔上,烘干、碾压后得正极极片;将正极、负极极片按照不同的电芯设计裁剪成相应尺寸,本实施例2电芯尺寸设计为SG'XSMW'XSCKmmnuWOr真空干燥除去溶剂和水分,备用;以Celgard 2400为隔膜,lmol/L的LiBFjMPC-EMC-DMC(体积比为 Nano ceramic powder fast ion conductor Li1OGeP2S12 D50 to 0.103μ, the binder according to a mass ratio of 85:15, respectively, weighed, added to the organic solvent is fully mixed in NMP slurry into a negative electrode, the negative electrode paste in an inert atmosphere coated on the lithium foil, evaporate the solvent, after rolling to obtain the surface covered with the nano metal lithium fast ion conductor layer, a ceramic cathode; lithium iron phosphate positive electrode material, a conductive agent, a binder in accordance with 82: 8: 10 mass ratio was added to the NMP solvent fully mixed into the positive electrode slurry, the positive electrode slurry was applied on an aluminum foil, drying, rolling to obtain positive electrode sheets; positive electrode, negative electrode sheet was cut into a corresponding cell in accordance with different design size, Example 2 of the present embodiment is sized batteries SG'XSMW'XSCKmmnuWOr dried solvent was removed in vacuo and water use; in Celgard 2400 as the membrane, lmol / L of LiBFjMPC-EMC-DMC (volume ratio

I: 1:1)为电解液,组装锂离子电池,静置Sh。 I: 1: 1) as the electrolyte, a lithium ion battery is assembled, left Sh.

[0033] 测试条件同实施例1,测试结果:5C充放,电池容量为149mAh/g ;循环500次,容量保持率为87%。 [0033] Test conditions were the same as in Example 1, the test results: 5C charge and discharge, the battery capacity was 149mAh / g; 500 cycles, the capacity retention rate of 87%.

[0034] 实施例3 [0034] Example 3

将D50为0.05μ的纳米锂快离子导体陶瓷粉LaQ.5L1.5Ti03、粘结剂按照90:10质量比例,分别称取,加入到NMP溶剂中充分混合均匀成负极浆料,将负极浆料于惰性气氛中涂于锂箔上,挥发掉溶剂,碾压后得表面覆有纳米锂快离子导体陶瓷层的金属锂负极;将正极材料磷酸铁锂、导电剂、粘结剂按照82:8:10的质量比例加入到NMP溶剂中充分混合均匀成正极浆料,将正极浆料涂于铝箔上,烘干、碾压后得正极极片;将正极、负极极片按照不同的电芯设计裁剪成相应尺寸,本实施例3电芯尺寸设计为8(1')\34(胃)\50(!1)111111。120°(:真空干燥除去溶剂和水分,备用;以Celgard 2400为隔膜,Imo VL的LiBF^EC-EMC-DMC(体积比为1:1:1)为电解液,组装锂离子电池,静置8h。 The D50 of 0.05μ fast ion conductor nano ceramic powder LaQ.5L1.5Ti03, the binder mass ratio of 90:10, respectively, weighed, added to the NMP solvent fully mixed into a negative electrode slurry, the negative electrode slurry applied on the lithium foil in an inert atmosphere, evaporate the solvent, to obtain the rolling surface of lithium metal anode is coated with nano-ceramic fast ion conductor layer; lithium iron phosphate positive electrode material, a conductive agent, a binder according to 82: 8 : 10 by mass ratio was added to the NMP solvent is fully mixed into the positive electrode slurry, the positive electrode slurry was applied on an aluminum foil, drying, rolling the obtained positive electrode sheet; the positive electrode, negative electrode sheet in a different cell design cut to the appropriate size, cell size 3 Example 8 is designed to (1 ') \ 34 (stomach) \ 50 111111.120 ° (according to the present embodiment (a!): The solvent was removed in vacuo and water and dried, standby; Celgard 2400 as the membrane to , Imo VL of LiBF ^ EC-EMC-DMC (volume ratio of 1: 1: 1) as the electrolyte, a lithium ion battery is assembled, left 8h.

[0035] 测试条件同实施例1,测试结果为:5C充放,电池容量为146mAh/g ;循环500次,容量保持率为81%。 [0035] Test conditions were the same as in Example 1, the test results: 5C charge and discharge, the battery capacity was 146mAh / g; 500 cycles, the capacity retention rate was 81%.

[0036] 实施例4 [0036] Example 4

将D50为0.02μ的纳米锂快离子导体陶瓷粉Li7P3Sn、粘结剂按照85:15质量比例,分别称取,加入到NMP溶剂中充分混合均匀成负极浆料,将负极浆料于惰性气氛中涂于锂箔上,挥发掉溶剂,碾压后得表面覆有纳米锂快离子导体陶瓷层的金属锂负极;将正极材料磷酸铁锂、导电剂、粘结剂按照82:8:10的质量比例加入到NMP溶剂中充分混合均匀成正极浆料,将正极浆料涂于铝箔上,烘干、碾压后得正极极片;将正极、负极极片按照不同的电芯设计裁剪成相应尺寸,本实施例4电芯尺寸设计为8(1')\34(胃)\50(!1)111111。120°(:真空干燥除去溶剂和水分,备用;以Celgard 2400为隔膜,lmol/L的LiPF6/EC-EMC_DMC(体积比为1:1:1)为电解液,组装锂离子电池,静置8h。 The D50 of 0.02μ fast ion conductor nano ceramic powder Li7P3Sn, the binder according to 85:15 by mass ratio, were weighed, added to the NMP solvent fully mixed into a negative electrode slurry, the negative electrode paste in an inert atmosphere applied on the lithium foil, evaporate the solvent, to obtain the rolling surface of lithium metal anode is coated with nano-ceramic fast ion conductor layer; lithium iron phosphate positive electrode material, a conductive agent, a binder in accordance with 82: 8: 10 by mass was added to the NMP solvent ratio fully mixed into the positive electrode slurry, the positive electrode slurry was applied on an aluminum foil, drying, rolling to obtain positive electrode sheets; positive electrode, negative electrode sheet was cut into a size of a corresponding cell in accordance with different design 4 sized batteries, the present embodiment is a 8 (1 ') \ 34 (stomach) \ 50 111111.120 ° (: drying the solvent was removed in vacuo and water use; in Celgard 2400 as the membrane, lmol / L (1!) the LiPF6 / EC-EMC_DMC (volume ratio of 1: 1: 1) as the electrolyte, a lithium ion battery is assembled, left 8h.

[0037] 测试条件同实施例1,测试结果为:5C充放,电池容量为141mAh/g ;循环500次,容量保持率为82.7%。 [0037] Test conditions were the same as in Example 1, the test results: 5C charge and discharge, the battery capacity was 141mAh / g; 500 cycles, the capacity retention rate was 82.7%.

[0038] 对比例I [0038] Comparative Example I

以金属锂箔为负极;将正极材料、导电剂、粘结剂按照82:8:10的质量比例加入到NMP溶剂中充分混合均匀成正极浆料,将正极浆料磷酸铁锂涂于铝箔上,烘干、碾压后得正极极片;将正极、负极极片按照不同的电芯设计裁剪成相应尺寸,本对比例I电芯尺寸设计为8(T)\34(胃)\50(!1)111111。120°(:真空干燥除去溶剂和水分,备用;以Celgard 2400为隔膜,lmol/L的LiPF6/EC-EMC-DMC(体积比为1:1:1)为电解液,组装锂离子电池,静置8h。 In the metal lithium foil as an anode; a cathode material, a conductive agent, a binder 82 according to: NMP solvent were added to 10 mass ratio is sufficiently mixed into the positive electrode slurry, lithium iron phosphate positive electrode slurry was applied onto aluminum foil: 8 , drying, rolling to obtain positive electrode sheets; positive electrode, negative electrode sheet was cut into a size according to a respective different cell designs, the present Comparative Example I is sized batteries 8 (T) \ 34 (stomach) \ 50 ( ! 1) 111111.120 ° (: drying the solvent was removed in vacuo and water use; in Celgard 2400 as the membrane, lmol / L of LiPF6 / EC-EMC-DMC (volume ratio of 1: 1: 1) as electrolyte, the assembly a lithium ion battery, standing 8h.

[0039] 测试条件同实施例1,测试结果为:5C充放,电池容量为147mAh/g ;循环500次,容量保持率为62.1%。 [0039] Test conditions were the same as in Example 1, the test results: 5C charge and discharge, the battery capacity was 147mAh / g; 500 cycles, the capacity retention rate was 62.1%.

[0040]综上所述,本发明提供的一种高能量锂离子电池及其制备方法,本发明通过在金属锂表面涂覆了一层纳米锂快离子导体陶瓷层,不仅阻止了金属锂与电解液在充放电期间的副反应,而且抑制了金属锂枝晶的形成与生长,同时减小了保护膜对锂离子迀移的阻力,大幅减缓保护膜对电池阻抗的增加,从而能在保证了电池的循环安全性、提高电池使用寿命的同时,实现高能量密度输出,满足电动车续航里程的能量需求。 [0040] In summary, a high-energy lithium ion battery and its preparation method provided in the present invention, the present invention is coated by a layer of nano lithium fast ion conductor layer on the ceramic surface of metal lithium, metal lithium is prevented and only electrolyte side reactions during charging and discharging, but also inhibits the formation and growth of dendrite metal lithium, a protective film while reducing the lithium ions move Gan resistance, significant reduction of the protective film to increase the impedance of the battery, which can ensure cycle battery safety, improve battery life, while achieving high energy density output to meet the energy requirements of the electric vehicle mileage.

[0041]应当理解的是,本发明的应用不限于上述的举例,对本领域普通技术人员来说,可以根据上述说明加以改进或变换,所有这些改进和变换都应属于本发明所附权利要求的保护范围。 [0041] It should be appreciated that the present invention is applied is not limited to the above-described example, those of ordinary skill in the art, can be modified or converted according to the above description, all such modifications and variations shall fall within the appended claims of the invention protected range.

Claims (10)

1.一种高能量锂离子电池的制备方法,其特征在于,包括步骤: A、将纳米锂快离子导体陶瓷粉、粘接剂按照85〜90:10〜15质量比例加入到有机溶剂中充分混合均匀成负极浆料,将负极浆料于惰性气氛中涂于锂箔上,烘干后、碾压得表面覆有纳米锂快离子导体陶瓷层的负极极片; B、将正极材料、导电剂、粘结剂按照80〜85:5-10:7〜12的质量比例加入到溶剂中充分混合均匀成正极浆料,将正极浆料涂于铝箔上,烘干后、碾压得正极极片; C、将正极、负极极片按照不同的电芯设计裁剪成相应尺寸,真空干燥除去溶剂和水分,备用; D、将备用的正极、负极极片、隔膜和电解液组装锂离子电池,静置8〜1h; E、对锂离子电池进行化成,所述化成工步为0.0lO0.03C小电流充电至3.2-3.6V,0.05 00.1C充至3.8〜4.0V,以0.I〜0.3C放电至2.8-3.2V,充放循环2~4次; F、对化成好的锂离子 1. A method for preparing a high-energy lithium ion batteries, characterized by comprising the step of: A, fast ion conductor nano ceramic powder adhesive according 85~90: 10 ~ 15 by mass ratio was added to the organic solvent sufficiently mixed into a negative electrode slurry, the slurry was applied on the lithium foil negative electrode in an inert atmosphere, after drying, have rolling surfaces coated with a negative electrode tab fast ion conductor nano ceramic layer; B, the positive electrode material, a conductive agent, a binder according to 80~85: 7~12 added mass ratio of the solvent to sufficiently mixing a positive electrode slurry, the positive electrode slurry was applied on an aluminum foil, dried and then rolling to give a positive electrode: 5-10 sheet; C, the positive electrode, negative electrode sheet cut according to different cell size correspondingly designed, the solvent was removed in vacuo and water and dried, standby; D, the alternate positive electrode, a negative electrode plate, a separator and an electrolyte assembly of a lithium ion battery, standing 8~1h; E, into lithium ion batteries, the chemical conversion process step of charging current to 0.0lO0.03C 3.2-3.6V, 0.05 00.1C charge to 3.8~4.0V, to 0.I~0.3 C is discharged to 2.8-3.2V, the charging and discharging cycle 2 to 4 times; F, for a lithium ion into good 池静置5〜9天,进行容量、倍率、循环寿命测试,电压测试范围3.0V-4.2Vo 5~9 days standing pool, the capacity, rate, cycle life test, the test voltage range of 3.0V-4.2Vo
2.根据权利要求1所述的高能量锂离子电池的制备方法,其特征在于,步骤A中,所述纳米锂快离子导体陶瓷粉为Li1()GeP2S12、Li3N、La().5L1.ST1hLi7P3Snai1QSnPShLi11Si2PS12中的一种。 The production of high energy lithium ion battery according to claim 1, wherein, in step A, the fast ion conductor lithium nano ceramic powder of Li1 () GeP2S12, Li3N, La (). 5L1.ST1hLi7P3Snai1QSnPShLi11Si2PS12 in kind.
3.根据权利要求1所述的高能量锂离子电池的制备方法,其特征在于,步骤A中,所述纳米锂快离子导体陶瓷粉颗粒粒度为10〜200nm。 The production of high energy lithium ion battery according to claim 1, wherein, in step A, the fast ion conductor lithium nano ceramic powder particle size of 10~200nm.
4.根据权利要求1所述的高能量锂离子电池的制备方法,其特征在于,步骤A中,负极极片表面的纳米锂快离子导体陶瓷层厚度为I〜ΙΟμπι。 4. A method for preparing a high energy lithium ion battery according to claim 1, wherein, in step A, the negative electrode of lithium nano-ceramic fast ion conductor layer is the thickness of the electrode substrate surface I~ΙΟμπι.
5.根据权利要求1所述的高能量锂离子电池的制备方法,其特征在于,步骤B中,将正极材料、导电剂、粘结剂按照82:8:10的质量比例加入到溶剂中。 5. A method for preparing a high energy lithium ion battery according to claim 1, wherein, in step B, the positive electrode material, a conductive agent, a binder 82 according to: the mass added to the solvent of Comparative Example 10: 8.
6.根据权利要求1所述的高能量锂离子电池的制备方法,其特征在于,步骤B中,所述溶剂为NMP溶剂。 6. A method for preparing a high energy lithium ion battery according to claim 1, wherein, in step B, the solvent is NMP solvent.
7.根据权利要求1所述的高能量锂离子电池的制备方法,其特征在于,步骤D中,所述隔膜为Celgard 24000 The production of high energy lithium ion battery according to claim 1, wherein, in step D, the separator is Celgard 24000
8.根据权利要求1所述的高能量锂离子电池的制备方法,其特征在于,步骤D中,所述电解液为LiPF6/EC-EMC-DMC、LiAsF6/PC-EMC-DMC、LiBF4/MPC-EMC-DMC 中的一种。 8. A method for preparing a high energy lithium ion battery according to claim 1, wherein, in step D, the electrolyte is LiPF6 / EC-EMC-DMC, LiAsF6 / PC-EMC-DMC, LiBF4 / MPC one kind of -EMC-DMC.
9.根据权利要求1所述的高能量锂离子电池的制备方法,其特征在于,步骤E中,所述化成工步为0.02C小电流充电至3.4V,0.1C充至3.0V。 The method of preparing a high energy lithium ion battery according to claim 1, characterized in that, in step E, into the process step of 0.02C charging current to 3.4V, 0.1C charge to 3.0V.
10.—种高能量锂离子电池,其特征在于,采用如权利要求1〜9任一所述的高能量锂离子电池的制备方法制备而成。 10.- kinds of high-energy lithium ion battery, which is characterized in that a preparation process of high energy lithium ion battery according to any one of claims 1~9 prepared by.
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