CN1750296A - Lithium ion secondary battery negative pole and its preparing method and lithium secondary battery including said negative pole - Google Patents

Lithium ion secondary battery negative pole and its preparing method and lithium secondary battery including said negative pole Download PDF

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CN1750296A
CN1750296A CNA2004100514938A CN200410051493A CN1750296A CN 1750296 A CN1750296 A CN 1750296A CN A2004100514938 A CNA2004100514938 A CN A2004100514938A CN 200410051493 A CN200410051493 A CN 200410051493A CN 1750296 A CN1750296 A CN 1750296A
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lithium
lithium ion
secondary battery
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ion conductive
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CNA2004100514938A
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陈冠宗
周俊杰
张翠萍
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陈冠宗
周俊杰
张翠萍
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    • 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
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825Oxygenated metallic slats or polyanionic structures, e.g. borates, phosphates, silicates, olivines

Abstract

This invention discloses the negative of a Li ionic secondary battery, its preparation method and the battery containing said negative, among which, the negative includes: rhombic black phosphorus with orthogonal structure applied by an inorganic solid electrolyte crystal film in 20-5000 artificially

Description

锂离子二次电池的负极及其制备方法以及包含该负极的锂离子二次电池 A negative electrode and a lithium ion secondary battery comprising the negative electrode and a method of preparing a lithium ion secondary battery

技术领域 FIELD

本发明涉及一种锂离子二次电池的负极及其制备方法,以及包含该负极的锂离子二次电池。 The present invention relates to a lithium ion secondary battery and its preparation method of a negative electrode, and a lithium ion secondary battery comprising the negative electrode. 尤其涉及一种人工施加的无机固体电解质晶体膜,所述的晶体膜有良好的锂离子电导率并且与现有锂离子碳酸酯电解液能形成有效的SEI膜的锂离子二次电池的负极其制备方法以及包含该负极的锂离子二次电池。 More particularly, to an inorganic solid electrolyte is applied to an artificial crystal film, the crystalline film having good lithium ion conductivity and the conventional lithium ion capable of forming a carbonate electrolyte lithium ion secondary battery negative SEI film is extremely effective and a method of preparing a lithium ion secondary battery comprising the negative electrode.

背景技术 Background technique

当今社会是信息飞速发展的社会,讯速、准确、大量的存储和传输信息是信息时代的要求。 Today's society is the rapid development of the information society, rapidly and accurately, plenty of storage and transmission of information is the information age. 移动电话、笔记本电脑、掌上电脑等便携式电子设备的发展,对于重量轻,容量大的锂离子二次电池提出了更高的要求。 Development of portable electronic devices such as mobile phones, laptop computers, handheld computers, etc., for light-weight, high-capacity lithium ion secondary battery of a higher requirement. 目前商业锂离子二次电池负极材料通常采用的是石墨类碳材料,其不足之处是:1)、其理论比容量只有372mAh/g,因而限制了锂离子二次电池比容量的进一步提高;2)、振实密度小造成体积比能量低,其振实密度一般在0.8g/cm3。 Current commercial lithium ion secondary battery negative electrode material generally employed is a graphite-based carbon material, its shortcomings are: 1), the theoretical specific capacity of only 372mAh / g, thus limiting further improve lithium ion secondary battery capacity ratio; 2), a tap density of less than the lower energy resulting volume, which typically tap density 0.8g / cm3.

发明内容 SUMMARY

本发明所要解决的技术问题是提供一种锂离子二次电池的负极及其制备方法以及包含该负极的锂离子二次电池,该负极包含一层具有良好的锂离子电导率并且与碳酸酯电解液相容性好的无机固体电解质晶体薄膜。 The present invention solves the technical problem is to provide a lithium ion secondary battery comprising a negative electrode and the negative electrode and a method of preparing a lithium ion secondary battery, the negative electrode comprising a layer having excellent lithium ion conductivity and electrolysis with a carbonate good capacitive liquid crystal film of the inorganic solid electrolyte. 该锂离子二次电池负极可用一种简单方法制备。 The lithium ion secondary battery negative electrode prepared in a simple method is available.

本发明的技术解决措施如下:一种锂离子二次电池的负极,包括:具有正交结构的斜方黑磷;在黑磷上人工施加一层无机固体电解质晶体膜,所述晶体膜具有20-5000的厚度并且包括一种离子电导率至少1×10-10S/cm的锂离子传导物质。 Technical solutions of the present invention are as follows: a lithium ion secondary battery negative electrode, comprising: a black phosphorus orthogonal orthorhombic structure; crystal film layer of an inorganic solid electrolyte is applied to the artificial black phosphorus, having a crystal film 20 -5000 thickness and comprises an ionic conductivity of at least 1 × 10-10S / cm of the lithium ion conductive substance.

所述锂离子传导物质是LixPOy,其中,2<X<4和3<Y<5。 The lithium ion conductive substance is LixPOy, wherein, 2 <X <4 and 3 <Y <5.

所述锂离子传导物质是Li3PO4。 The lithium ion conductive substance is Li3PO4.

所述锂离子传导物质是LiaPObNC此处a为2-4,b为3-5,c为0.1-0.9。 The lithium ion conductive substance is a LiaPObNC here is 2-4, b is 3-5, c is 0.1 to 0.9.

所述锂离子传导物质是Li2.9PO3.3N0.46。 The lithium ion conductive substance is Li2.9PO3.3N0.46.

一种制备锂离子二次电池负极的方法,在强氧化剂溶液里,将黑磷进行进氧化处理,与含锂的化合物作用沉积一层固体电解质晶体膜,所述晶体膜含有一种离子电导率至少为1×10-10s/cm的锂离子传导物质;强氧化剂选自包括过硫酸铵、硝酸、过氧化氢和硫酸;含锂化合物选自包括正丁基锂、叔丁基锂、六氟磷锂、四氟硼酸锂、柠檬酸锂、锂萘和氢氧化锂。 A method for the lithium ion secondary battery negative electrode preparation, the strong oxidant solution, and phosphorous into the black oxide treatment, the solid electrolyte layer with the crystal film deposited lithium-containing compound on the conductivity of an ionic crystal film comprising at least 1 × 10-10s / cm of the lithium ion conductive substance; strong oxidant selected from the group comprising ammonium persulfate, nitric acid, hydrogen peroxide and sulfuric acid; lithium-containing compound selected from the group comprising n-butyllithium, t-butyllithium, hexafluoro lithium phosphate, lithium tetrafluoroborate, lithium citrate, lithium hydroxide and lithium naphthalene.

上述锂离子传导物质是LixPOy,其中,2<X<4和3<Y<5。 The lithium ion conductive substance is LixPOy, wherein, 2 <X <4 and 3 <Y <5.

上述锂离子传导物质是Li3PO4。 The lithium ion conductive substance is Li3PO4.

一种锂离子二次电池,其负极是在黑磷基材上沉积有一层具有20-5000的厚度并且含有一种离子电导率至少为1×10-10s/cm的锂离子传导物质的晶体膜;正极包括一种选自由钴酸锂、镍酸锂、锰酸锂、钴镍酸锂、镍锰酸锂、磷酸铁锂、磷酸钴锂其中的任何一种或两种以上任意比例的组合;电解液的主盐可以是六氟磷酸锂、四氟硼酸锂、六氟砷酸锂、高氯酸锂、全氟烷基磺酸锂其中的一种;溶剂成分可以是乙烯碳酸酯、碳酸二甲酯、碳酸二乙酯、丙烯碳酸酯、二碳酸甲乙酯、碳酸甲丙酯、二乙氧基乙烷、2-甲基四氢呋喃中的一种或两种以上任意比例的组合。 A lithium ion secondary battery, a negative electrode layer having a thickness 20-5000 deposited on a substrate and black phosphorus containing at least one ionic conductivity of the crystal 1 × 10-10s / cm lithium ion conductive substance film; includes one positive electrode consisting of lithium cobalt oxide in any ratio, lithium nickelate, lithium manganate, lithium cobalt nickel oxide, lithium nickel manganese oxide, lithium iron phosphate, lithium cobalt phosphate wherein any one or a combination of two or more selected from ; main electrolyte salt may be lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium perfluoroalkyl sulfonic acid wherein one; solvent component may be ethylene carbonate, dimethyl carbonate , diethyl carbonate, propylene carbonate, diethylene carbonate, methyl ethyl carbonate, methyl propyl carbonate, diethoxyethane, tetrahydrofuran, 2-methyl any ratio or a combination of two or more.

本发明的突出效果是:1)、与传统的碳负极相比它的比容量可以大大地提高达到700mAh/g;2)、振实密度大,密度一般在1.27g/cm3,这样便于电池可以提高体积比能量。 Highlight the effect of the present invention are: 1), and the conventional carbon negative electrode can greatly improve reached 700mAh / g compared to its specific capacity; 2), tap density, density is generally at 1.27g / cm3, the battery can be so easy increasing the volume ratio of the energy.

附图说明 BRIEF DESCRIPTION

图1为本发明黑磷负极无晶体膜时的充放电曲线图;图2为本发明黑磷负极沉积了LiaPObNC晶体膜后的第二次充放电曲线图;图3为本发明黑磷负极无晶体膜充放电后的XRD图谱; Figure 1 is a graph showing the charge-discharge time of no black phosphorus crystal film anode invention; FIG. 2 of the present invention, the negative black phosphorus is deposited a second graph showing the charge-discharge LiaPObNC crystal film; FIG. 3 of the present invention, no negative black phosphorus XRD pattern of the crystal film after the charging and discharging;

图4为本发明黑磷负极无晶体膜充放电前的XRD图谱;图5为本发明黑磷负极沉积了Li3PO4晶体膜后的第二次充放电曲线图。 FIG 4 XRD pattern of black phosphorus negative electrode before charge and discharge of non-crystal film of the present invention; FIG. 5 black phosphorus present invention, the negative electrode is deposited a second graph showing the charge-discharge Li3PO4 crystal film.

具体实施方式 Detailed ways

实施例1将200目过筛的5克黑磷粉末放入100毫升的强氧化剂浓度为10%的硝酸(HNO3)溶液中在常温下进行氧化处理10小时,然后再用蒸馏水洗涤,然后放入干燥箱中在120℃下烘干12小时。 Example 1 A 200 mesh sieve 5 g of a black powder was placed in 100 ml of phosphorus strong oxidizing agent concentration of 10% nitric acid (of HNO3) solution for oxidation at room temperature for 10 hours and then washed with distilled water and then placed oven dried at 120 ℃ 12 hours. 然后再以偏二氟乙烯为粘结剂、N-甲基吡咯烷酮为有机溶剂,乙炔黑为导电剂,按黑磷∶乙炔黑∶偏二氟乙烯=90∶4∶6比例混合搅拌均匀浆料涂布在集流体铜箔上,120℃下烘干16小时。 Then to vinylidene fluoride as a binder, N- methylpyrrolidone as an organic solvent, acetylene black as a conductive agent, phosphorous by black: acetylene black: polyvinylidene fluoride = homogeneous slurry mixing ratio 90:4:6 It was coated on a copper foil current collector, dried at 120 ℃ 16 hours. 然后浸渍在任意比例的含锂化合物正丁基锂/乙烷溶液里12小时,再用一二甲氧乙烷洗涤后放入真空干燥箱内将程序升温到160℃,保温48小时即得本发明所需的锂离子二次电池负极。 Then immersed in the lithium-containing compound in any ratio of n-butyllithium / hexane solution was 12 hours, and then washed with dimethoxyethane after twelve placed in a vacuum oven to 160. The temperature program deg.] C, incubated 48 hours to obtain the present lithium ion secondary battery negative electrode of the present invention required.

将上述制得的锂离子二次电池负极,正极材料为钴酸锂、电解液为六氟磷酸锂、溶剂为乙烯碳酸酯和碳酸二乙酯,体积比为1∶1,隔膜为CeLgrd2300微孔膜,制成063048电池,测定该电池的容量为1385mAh。 The above-obtained lithium ion secondary battery negative electrode, a positive electrode material is lithium cobalt oxide, lithium hexafluorophosphate as an electrolyte, a solvent of ethylene carbonate and diethyl carbonate, a volume ratio of 1, the separator is a microporous membrane CeLgrd2300, Ltd. 063,048 into the battery, the battery capacity was measured 1385mAh.

实施例2将上述制得的锂离子二次电池负极,正极材料为锰酸锂,电解液为六氟硼酸锂,溶剂为乙烯碳酸酯和碳酸二乙酯体积比为1∶3,隔膜为CeLgrd2300微孔膜,制成063048电池。 Example 2 The above-prepared negative electrode lithium ion secondary battery positive electrode material lithium manganese oxide, lithium hexafluorophosphate as an electrolyte, a solvent of ethylene carbonate and diethyl carbonate 1:3 volume ratio, a separator is CeLgrd2300 microporous membrane made of 063 048 cells. ,测定该电池的容量为1345mAh。 , Measurement of the battery capacity is 1345mAh.

实施例3将上述制得的锂离子二次电池负极,正极材料为镍酸锂、电解液为氯酸酸锂、溶剂溶剂为乙烯碳酸酯和碳酸二乙酯,体积比为1∶1,隔膜为CeLgrd2300微孔膜,制成063048电池,测定该电池的容量为1425mAh。 Example 3 The above-prepared negative electrode lithium ion secondary battery positive electrode material of lithium nickelate, lithium chloride electrolyte is sour, solvent is a solvent of ethylene carbonate and diethyl carbonate, a volume ratio of 1, the membrane CeLgrd2300 is a microporous membrane made of 063 048 cell, measurement of the battery capacity is 1425mAh.

实施例4: Example 4:

在惰性气体气氛下,利用一个靶将晶体沉积到黑磷电极上,所述的晶体膜包括一种锂离子电导率至少为1×10-10S/cm锂离子传导物质。 Under an inert gas atmosphere, using a target will be deposited onto the crystal electrode black phosphorus, said film comprising a crystal of a lithium ion conductivity of at least 1 × 10-10S / cm lithium ion conductive substance.

所述锂离子传导物质是LixPOy,其中,2<X<4和3<Y<5所表示的化合物,并且在氮气气氛下它是稳定的。 The lithium ion conductive substance is LixPOy, wherein 2 <and 3 <Y <compound represented by X <4 5, under a nitrogen atmosphere and it is stable.

所述锂离子传导物质是LiaPObNC此处a为2-4,b为3-5,c为0.1-0.9。 The lithium ion conductive substance is a LiaPObNC here is 2-4, b is 3-5, c is 0.1 to 0.9.

惰性气体选自氦气、氖气以及氩气,因为上述气体都不会同黑磷发生化学反应产生副产物。 The inert gas is selected from helium, neon and argon, as the gas does not react chemically together with black phosphorus by-product.

所述靶可以是Li3PO4或者以适当混合比例混合的Li2O和P2O5的混合物。 The target may be a mixture or Li3PO4 mixed at an appropriate mixing ratio of Li2O and P2O5.

在压力为5毫托,射频功率为300W以及氩气气氛下,使用直径为4英寸的Li3PO4靶在黑磷电极沉积10分钟形成一层Li3PO4晶体膜所述沉积过程通过适宜的方法进行,例如:镀、电子束蒸发,真空热蒸发,激光烧蚀,化学汽相沉积,热蒸发、等离子体化学汽相沉积、激光化学汽相沉积或者喷射汽相沉积。 At a pressure of 5 mTorr, RF power of 300W and an argon atmosphere, a diameter of 4 inches by suitable method to form a layer Li3PO4 target Li3PO4 crystal film deposition process of the black phosphorus electrodeposition for 10 minutes, for example: plating, electron beam evaporation, vacuum thermal evaporation, laser ablation, chemical vapor deposition, thermal evaporation, plasma chemical vapor deposition, laser chemical vapor deposition, or jet vapor deposition. 相关领域技术人员可以理解,所述沉积并不局限于上述方法,它包括任何常规的方法。 Skilled in the relevant art can be appreciated, the deposition method is not limited to the above, which comprises any conventional method.

将未经处理的黑磷作为负极,金属锂片为对电极,隔膜为CeLgrd2300微孔膜,电解液为1.0mol/L,LiPF6/EC∶DEC,溶剂体积比为1∶1,在相对湿度小1%的手套箱中制成模拟电池,测定黑磷充放电性能其结果见图1。 The untreated black phosphorus as the negative electrode, metal lithium sheets as the counter electrode, the separator is a microporous membrane CeLgrd2300, the electrolytic solution was 1.0mol / L, LiPF6 / EC:DEC, solvent volume ratio of 1, the relative humidity was low 1% to prepare a simulated cell in a glove box, black phosphorus charge-discharge characteristics measured result shown in Fig. 图1中由于在0.8伏未形成有效的SEI膜,致使溶剂分子发生共嵌入,放电容量图中显示为零。 In FIG. 1 due to the effective SEI film is not formed at 0.8 volts, so that the solvent molecules were fitted, the discharge capacity is shown as zero in FIG.

将上述方法制得的黑磷电极为负极,金属锂片为对电极,隔膜为CeLgrd2300微孔膜,电解液为1.0mol/L,LiPF6/EC∶DEC,溶剂体积比为1∶1,在相对湿度小1%的手套箱中制成机式模拟电池,测定黑磷充放电性能其结果见图2、图5。 The black phosphorus electrode prepared as described above for the negative electrode, metal lithium sheets as the counter electrode, the separator is a microporous membrane CeLgrd2300, the electrolytic solution was 1.0mol / L, LiPF6 / EC:DEC, solvent volume ratio of 1, the relative 1% moisture in a glove box to prepare a small machine analog battery, charge-discharge characteristics black phosphorus measured results of FIG 2, FIG 5. 从图2、5可以看出本发明的负极能进行有效的充放电循环、放电容量图2中为630mAh/g。 As can be seen from FIGS. 2, 5 negative electrode of the present invention can effectively charge and discharge cycles, the discharge capacity in FIG. 2 is 630mAh / g. 图5中V表示电压,C表示比容量。 5 represents the voltage V, C represents the ratio of capacity.

测试条件: Test Conditions:

充放电电流密度、充电电流1mA/cm2、放电电流1mA/cm2截止电压0-1.0伏。 Charge-discharge current density, the charging current 1mA / cm2, a discharge current of 1mA / cm2 cut-off voltage of 0-1.0 volts. 实验结果表明黑磷电极经过人工沉积晶体膜后,首次充电时在0.8伏形成一个电压平台,对应的是在晶体膜上附着一层致密有效的SEI膜。 The results show that black phosphorus electrode through artificial crystal film deposition, when the first charge is formed at a voltage of 0.8 volts platform, attached to a layer corresponding to the active dense SEI film crystal film. 由于该SEI膜的形成阻止了有机分子的共嵌入,放电容量大于650mAh/g。 Due to the formation of the SEI film prevents organic molecules were fitted, larger discharge capacity than 650mAh / g. 未经沉积晶体薄膜的黑磷电极没有形成有效的SEI膜,溶剂分子发生共嵌入,使黑磷结构发生根本性的破坏,放电容量为零。 Black phosphorus electrode without deposition of crystals in the film is not a valid SEI film is formed, the solvent molecules were embedded in the black phosphorus fundamental structural damage occurs, the discharge capacity is zero. 图3为没有沉积晶体膜充电后的XRD图谱。 Figure 3 is a XRD pattern of the deposited no crystal film charging.

工作原理:黑磷具有像石墨一样的层状结构,层面内原子以σ共价键叠加,相互牢固结合,二层间仅以弱的范德华力连接,这种混合键型的晶体结构使其具有特殊的化学性质,既一些原子、分子可以嵌入到这类晶体层面间,并不破坏堆垛的共价键,仅使层间距发生变化,生成层间化合物。 Working principle: black phosphorus as having the same layered structure of graphite, the atoms to level σ covalent bond superimposed, are firmly bound, only weak van der Waals forces between the floor connection, this mixed key type crystal structure so as to have special chemical properties, both some of the atoms, molecules may be embedded between the level of such crystals, the stack does not destroy the covalent bond, only the layer spacing changes between the generating layer compound. 石墨中,一个碳原子以配位数为3形成σ共价键,仅余下一个P电子参与形成离域π键,而黑磷中,磷原子以配位数为3形成σ共价键后,有一对孤P电子参与形成离域π键。 Graphite, a carbon atom to form a coordination number of 3 σ covalent bond, only one P remaining after participating in delocalized π electron bond and black phosphorus, the phosphorus atom to form a coordination number of 3 σ covalent bond, P has one lone electron delocalized π bond involved in the formation. 这说明黑磷能够提供更多的与锂离子配位的成键电子。 This indicates black phosphorus bonding electrons can be provided with additional lithium ions coordinated. 黑磷比石墨具有更高比容量的可能性。 Black phosphorus with higher specific capacities than graphite possibility. 黑磷负极在以丙烯碳酸酯、乙烯碳酸酯等碳酸酯电解液体系中,首次充电并不能形成有效的SEI膜,致使溶剂分子发生共嵌入,根本性的破坏了黑磷晶体结构,使黑磷电极因此失去活性。 Black phosphorus negative electrode in a propylene carbonate, ethylene carbonate and the like carbonates electrolyte system, the first charge can not form an effective SEI film, so that the solvent molecules were embedded, black phosphorus radical destroys crystal structure of the black phosphorus electrodes lose activity. 但正交结构的斜方黑磷;在黑磷上人工施加一层无机固体电解质晶体膜,所述晶体膜具有20-5000的厚度并且包括一种离子电导率至少1×10-10S/cm锂离子传导物质后,实验证明首次充电在黑磷基材表面沉积晶体膜的负极能形成有效的SEI膜,阻止由于溶剂锂离子的共嵌入而导致的黑磷结构崩溃现象的发生。 However, the structure of the orthogonal orthorhombic black phosphorus; one inorganic phosphorus on the black crystalline solid electrolyte membrane applied manually, a crystal film having a thickness of 20-5000 and comprises an ionic conductivity of at least 1 × 10-10S / cm after the lithium ion conductive materials, experiments show that the initial charge in the base surface of the negative black phosphorus deposited crystal film can form an effective SEI film prevents black phosphorus embedded structure due to co-solvent lithium ions caused the collapse phenomenon occurs. 而它允许锂离子从其中通过。 And it allows lithium ions to pass therethrough.

本发明的实施例1中黑磷粉末在强氧化剂的作用下表面会形成磷的氧化物和酸,经蒸溜水洗涤后,残留在黑磷表面的氧化物在有水和氧的条件下加热干燥,其表面会生成少量的磷酸,由于磷酸和含锂的化合物作用会在黑磷颗粒的表面形成一层Li3PO4的晶体膜。 After embodiments of the present invention in a black phosphorus powder surface will form a phosphorus oxide and an acid under the action of a strong oxidizing agent, by distilled water washing, remaining in the black phosphorus oxide surface was heated and dried under conditions of oxygen and water , its surface will generate a small amount of phosphoric acid, due to the action of phosphoric acid compound containing lithium and Li3PO4 crystal film layer is formed on the surface of particles of black phosphorus.

Claims (9)

1.一种锂离子二次电池的负极,其特征在于:包括:具有正交结构的斜方黑磷;在黑磷上人工施加一层无机固体电解质晶体膜,所述晶体膜具有20-5000的厚度并且包括一种离子电导率至少1×10-10S/cm的锂离子传导物质。 A lithium ion secondary battery negative electrode, characterized by: comprising: orthogonal orthorhombic structure having a black phosphorus; crystal film layer of an inorganic solid electrolyte is applied to the artificial black phosphorus, a crystal film having 20-5000  thickness and comprises an ionic conductivity of at least 1 × 10-10S / cm of the lithium ion conductive substance.
2.根据权利1所述的负极,其特征在于:锂离子传导物质是LixPOy,其中,2<X<4和3<Y<5。 2. The anode according to claim 1, wherein: the lithium ion conductive substance is LixPOy, wherein, 2 <X <4 and 3 <Y <5.
3.根据权利要求2所述的负极,其特征在于:锂离子传导物质是Li3PO4。 3. The anode according to claim 2, wherein: the lithium ion conductive substance is Li3PO4.
4.根据权利要求1所述的负极,其特征在于:锂离子传导物质是LiaPObNC此处a为2-4,b为3-5,c为0.1-0.9。 4. The anode according to claim 1, wherein: the lithium ion conductive substance is a LiaPObNC here is 2-4, b is 3-5, c is 0.1 to 0.9.
5.根据权利要求4所述的负极,其特征在于:锂离子传导物质是Li2.9PO3.3N0.46。 The negative electrode as claimed in claim 4, wherein: the lithium ion conductive substance is Li2.9PO3.3N0.46.
6.一种制备锂离子二次电池负极的方法,其特征在于:在强氧化剂溶液里,将黑磷进行进氧化处理,与含锂的化合物沉积一层固体电解质晶体膜,所述晶体膜含有一种离子电导率至少为的1×10-10s/cm锂离子传导物质;强氧化剂选自包括过硫酸铵、硝酸、过氧化氢和硫酸;含锂化合物选自包括正丁基锂、叔丁基锂、六氟磷锂、四氟硼酸锂、柠檬酸锂、锂萘和氢氧化锂。 A method for a lithium ion secondary battery negative electrode preparation, characterized in that: the strong oxidant solution, the phosphorous into the black oxide treatment, a lithium-containing compound is deposited and the solid electrolyte layer crystal film, the film contains crystals at least one ionic conductivity of 1 × 10-10s / cm lithium ion conductive substance; strong oxidant selected from the group comprising ammonium persulfate, nitric acid, hydrogen peroxide and sulfuric acid; lithium-containing compound selected from the group comprising n-butyllithium, tert-butyl butyl lithium, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium citrate, lithium hydroxide and lithium naphthalene.
7.根据权利6所述的方法,其特征在于:锂离子传导物质是LixPOy,其中,2<X<4和3<Y<5。 The method according to claim 6, wherein: the lithium ion conductive substance is LixPOy, wherein, 2 <X <4 and 3 <Y <5.
8.根据权利要求6所述的方法,其特征在于:锂离子传导物质是Li3PO4 The method according to claim 6, wherein: the lithium ion conductive substance is Li3PO4
9.一种锂离子二次电池,其特征在于:其负极是在黑磷基材上沉积有一层具有20-5000的厚度并且含有一种离子电导率至少为1×10-10S/cm的锂离子传导物质的晶体膜;正极包括一种选自由钴酸锂、镍酸锂、锰酸锂、钴镍酸锂、镍锰酸锂、磷酸铁锂、磷酸钴锂其中的任何一种或两种以上任意比例的组合;电解液的主盐可以是六氟磷酸锂、四氟硼酸锂、六氟砷酸锂、高氯酸锂、全氟烷基磺酸锂其中的一种;溶剂成分可以是乙烯碳酸酯、碳酸二甲酯、碳酸二乙酯、丙烯碳酸酯、二碳酸甲乙酯、碳酸甲丙酯、二乙氧基乙烷、2-甲基四氢呋喃中的一种或两种以上任意比例的组合。 A lithium ion secondary battery, comprising: a negative electrode layer having a thickness 20-5000 deposited on a substrate and black phosphorus containing an ionic conductivity of at least 1 × 10-10S / cm of a lithium ion conductive crystal film material; positive electrode comprises one selected from the group consisting of lithium cobaltate, lithium nickelate, lithium manganate, lithium cobalt nickel oxide, lithium nickel manganese oxide, lithium iron phosphate, lithium cobalt phosphate wherein any one or two combinations in any proportion above; a main electrolyte salt may be lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium perfluoroalkyl sulfonic acid wherein one; solvent component may be ethylene carbonate carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate, diethylene carbonate, methyl ethyl carbonate, methyl propyl carbonate, diethoxyethane, 2-methyltetrahydrofuran in one kind or two or more in any ratio combination.
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CN107482173A (en) * 2017-06-21 2017-12-15 深圳大学 A negative electrode active material for a lithium ion battery, a preparing method thereof, a negative electrode plate of the lithium ion battery and the lithium ion battery

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