CN107221637A - A kind of laser ablation oxidation in-situ preparation method of the integrated negative pole of lithium ion battery - Google Patents

A kind of laser ablation oxidation in-situ preparation method of the integrated negative pole of lithium ion battery Download PDF

Info

Publication number
CN107221637A
CN107221637A CN201710375337.4A CN201710375337A CN107221637A CN 107221637 A CN107221637 A CN 107221637A CN 201710375337 A CN201710375337 A CN 201710375337A CN 107221637 A CN107221637 A CN 107221637A
Authority
CN
China
Prior art keywords
negative pole
metal
integrated negative
metal oxide
tinsel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710375337.4A
Other languages
Chinese (zh)
Other versions
CN107221637B (en
Inventor
汪长安
梁芃
苏博
苏一博
钟敏霖
张红军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tsinghua University
Original Assignee
Tsinghua University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tsinghua University filed Critical Tsinghua University
Priority to CN201710375337.4A priority Critical patent/CN107221637B/en
Publication of CN107221637A publication Critical patent/CN107221637A/en
Application granted granted Critical
Publication of CN107221637B publication Critical patent/CN107221637B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Tinsel, is first cleaned by ultrasonic by a kind of laser ablation oxidation in-situ preparation method of the integrated negative pole of lithium ion battery respectively using alcohol or acetone and deionized water；Under room temperature and air atmosphere, irradiation tinsel is scanned respectively using ps pulsed laser and ns pulsed laser, laser vertical obtains the integrated negative pole of metal oxide metal in tinsel；The integrated negative pole of metal oxide metal is put into vacuum drying chamber again and dried；Finally the integrated negative pole of dried metal oxide metal is soaked in the mixed solution of butyl titanate and absolute ethyl alcohol, then hydrolyze naturally in atmosphere, dry in an oven, obtain the integrated negative pole of modified metal oxide metal, used as lithium ion battery negative material, outstanding discharge and recharge long circulating stability and excellent chemical property are presented, the present invention has the advantages that simple and efficient, low cost.

Description

A kind of laser ablation oxidation in-situ preparation method of the integrated negative pole of lithium ion battery
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of laser of the integrated negative pole of lithium ion battery burns Erosion oxidation in-situ preparation method.
Background technology
With to the growing of moving electronic components and lithium ion battery demand, efficient and inexpensive manufacture lithium from Some problems have been engendered in terms of sub- GND.For example, low theoretical capacity and complexity due to being commercialized graphite cathode Preparation process, it occurs in that increasing limitation.Therefore, the high efficiency preparation method of development negative electrode of lithium ion battery and exploitation Advanced negative material seems very necessary, is also a huge challenge.In the last few years, transition metal oxide, for example Cu2O/CuO,Fe2O3With NiO etc., due to its high theoretical capacity, low cost and extensive reserve distribution, obtain increasing Concern.In conventional research, different-shape, different types of transition metal oxide as lithium ion battery negative material, Show excellent stability and chemical property.
However, in the charge and discharge process of lithium ion battery, with the progress of negative material embedding and removing, metal oxidation Thing negative pole will produce larger volumetric expansion and contraction, cause negative active core-shell material to be come off from collector and reduce conduction Property.In addition, it is necessary to negative material is bonded on electrode current collecting body using polymeric binder (such as vinylidene fluoride PVDF), But there are some researches show polymeric binder can accelerate loss and the reduction cyclical stability of irreversible capacity.In order to solve this Problem, people attempt the direct growth in situ negative active core-shell material on a current collector of a variety of methods, due to being in metal collector Original position prepares integrated negative pole, it is not necessary to binding agent, so the negative pole also has more preferable electron conduction and structural stability. Integrated negative material is such as prepared come in situ in metal collector using electro-deposition, chemical vapor deposition or hydro-thermal method, still The problem of all these methods can all have this or that, than if desired for expensive equipment, complicated preparation process and high Manufacturing cost etc., limit its large-scale application in actual Lithium Battery Industry.Therefore, develop a kind of extensive, simple Efficiently, cost effective method prepare the integrated negative pole of binder free with good chemical property be in the urgent need to.
The content of the invention
In order to overcome the shortcoming of above-mentioned prior art, object of the present invention is to provide a kind of integration of lithium ion battery Negative pole laser ablation oxidation in-situ preparation method, prepared by nanosecond laser one-step method, negative metal (such as Cu, Fe, Ni, W, Mo etc.) growth in situ goes out to have the metal oxide active material of unique porosity and looseness nanotopography on collector, pass through Later stage coating modification, is used as lithium ion battery negative material, present outstanding discharge and recharge long circulating stability and Excellent chemical property, has the advantages that simple and efficient, low cost.
In order to achieve the above object, the technical scheme taken of the present invention is：
A kind of laser ablation oxidation in-situ preparation method of the integrated negative pole of lithium ion battery, comprises the following steps：
1) tinsel is cleaned by ultrasonic 30 minutes respectively using alcohol or acetone and deionized water, the impurity on surface is clear Remove；Tinsel is copper, iron, nickel, tungsten or molybdenum, and purity reaches more than 99.99%；
2) under room temperature and air atmosphere, irradiation tinsel, optical maser wavelength are scanned respectively using ps pulsed laser and ns pulsed laser 532nm, 1000~30000Hz of pulse frequency, 1~100ns of pulsewidth, single pulse energy 0.1~10 × 10-4J, laser scanning surface speed 5~300mm s-1, laser vertical obtains the integrated negative pole of metal oxide-metal in tinsel；
3) the integrated negative pole of metal oxide-metal is put into 60~90 DEG C of dry 6~12h in vacuum drying chamber；
4) by the integrated negative pole of dried metal oxide-metal in the mixed of butyl titanate (TBOT) and absolute ethyl alcohol Close in solution and soak 1~60 second, the volume ratio 1 of butyl titanate (TBOT) and absolute ethyl alcohol:5~1:5000；Then in air Middle to hydrolyze naturally 1~10 minute, 60-90 DEG C of drying 6-12h, obtains modified metal oxide-metal integration in an oven Negative pole；Described butyl titanate (TBOT) is pure to analyze.
The integrated negative pole of modified metal oxide-metal is washed into diameter 1.2cm disks using sheet-punching machine, its is direct It is used as negative electrode of lithium ion battery；Then, lithium metal is as to electrode and reference electrode, and uses Celgard barrier films and dissolving EC/DMC/DEC, 1:1:1vol% 1M LiPF6As electrolyte, button cell is assembled in argon gas atmosphere glove box.
Beneficial effects of the present invention are：
The present invention uses laser ablation oxidizing process, by controlling the different parameters of laser, using nanosecond laser directly in gold Belong to the integrated lithium ion battery of the metal oxide-metal for preparing the binder free with certain nanostructured in situ on collector Negative pole.In room temperature and air, metal collector is irradiated using nanosecond laser, in high temperature of the laser to metal base surface and play Under strong effect, growth in situ goes out one layer of metal oxide with unique nanostructured, and and metal on the matrix of collector Matrix is combined closely.On this basis, TiO is carried out to the oxide surface of formation using cladding process2Coating modification is handled, will The integrated material is used as negative electrode of lithium ion battery, presents stable long circulation life and good chemical property. With the method for the present invention, original position is successfully prepared with excellent electrochemical in the metal collectors such as copper, iron, nickel, tungsten, molybdenum respectively The CuO of performancex-Cu、FexOy-Fe、NixOy-Ni、WO3-W、MoO3The metal oxide-metal such as-Mo integrated composite is born Pole.Demonstrate the universality and huge application and economic prospect of the advanced preparation technology.
The commercial negative pole copper current collector of lithium ion battery is directly handled using laser, binder free nanometer cotton shape is obtained CuOx- Cu integration negative poles.Laser various parameters are controlled, the copper foil surface of ablation is uniformly grown one layer of cotton shape and receives Rice CuOxStructure, the short texture is porous, and specific surface area is high, can alleviate the enormousness change produced in charge and discharge process, Be conducive to contact of the electrolyte with negative active core-shell material.The integrated negative pole is used as negative electrode of lithium ion battery, is presented existing Go out the chemical properties such as stable charge and discharge cycles ability, high power capacity, good high rate performance.Compared to prior art, the work Integrated negative pole prepared by skill is more efficient, and cost is lower, can prepare on a large scale, while having good electrochemistry. 1.5A g-1High current density under, after circulation 800 times, coulombic efficiency remains at more than 99%, and the 800th circulation is put Capacitance is 393.6mAh g-1, compared to the capacity 453.3mAh g of second of circulation-1, its capability retention is 87%.
Fe paper tinsels, Ni paper tinsels and W paper tinsels are directly handled respectively using laser, have obtained FexOy-Fe、NixOy- Ni and WO3- W integrations Negative material, shows the chemical properties such as stable charge and discharge cycles ability, high power capacity, good high rate performance.For example, FexOyAfter-Fe integration negative poles material circulation 300 times, in 0.24mA cm-2Stable discharge capacity is showed under current density 0.25mAh cm-2, in 0.36mA cm-2Current density discharge capacity 0.18mAh cm-2, coulombic efficiency is all higher than 99%, and And in 1.0mA cm-2After lower 1000 circulations of current density, discharge capacity still reaches 0.14mAh cm-2。NixOy- Ni integrations After negative pole is circulated 400 times, in 0.24mA cm-2Current density discharge capacity reaches 0.18mAh cm-2, in 0.36mA cm-2Electricity Under current density, discharge capacity reaches 0.175mAh cm-2, coulombic efficiency is all higher than 99%.WO3- W integration negative poles are in 0.20mA cm-2Current density under, by 200 circle charge and discharge cycles, discharge capacity is stable in 0.60mAh cm-2。
It is this that directly to handle metal collector with laser to prepare the method for metal oxide-metal composite negative pole be one The method for planting universality, can also be applied on other sheet metals, be a kind of method efficiently, easy, inexpensive, Ke Yi great Sizable application.
Brief description of the drawings
Fig. 1 (a-d) is the SEM image of the integrated negative poles of CuO-Cu under the different enlargement ratios of embodiment 1；(e-h) it is implementation The TEM image of the integrated negative poles of CuO-Cu under the different enlargement ratios of example 1.
Fig. 2 is the X ray diffracting spectrum of the integrated negative poles of CuO-Cu of embodiment 1.
Fig. 3 (a) is high rate performance of the integrated negative poles of CuO-Cu of embodiment 1 under different current densities；(b, c) is real Apply cycle performance of the integrated negative poles of CuO-Cu of example 1 under different current densities.
Fig. 4 is without (right, CuO-Cu integrations negative pole) pictorial diagram after laser treatment (left, copper foil) and laser treatment.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in detail.
Embodiment one
A kind of laser ablation oxidation in-situ preparation method of the integrated negative pole of lithium ion battery, comprises the following steps：
1) tinsel is cleaned by ultrasonic 30 minutes respectively using alcohol and deionized water, the impurity on surface is removed；Gold Category paillon foil is copper, and purity reaches more than 99.99%, 100 μm of thickness；
2) under room temperature and air atmosphere, irradiation tinsel, optical maser wavelength are scanned respectively using ps pulsed laser and ns pulsed laser 532nm, pulse frequency 30000Hz, pulsewidth 10ns, single pulse energy 1.5 × 10-4J, laser scanning surface speed 25mm s-1, laser Perpendicular to tinsel, the integrated negative pole of metal oxide-metal is obtained；
3) the integrated negative pole of metal oxide-metal is put into 60 DEG C of dry 6h in vacuum drying chamber；
4) by the integrated negative pole of dried metal oxide-metal in the mixed of butyl titanate (TBOT) and absolute ethyl alcohol Close in solution and soak 50 seconds, the volume ratio 1 of butyl titanate (TBOT) and absolute ethyl alcohol:5000；Then Natural Water in atmosphere Solution 5 minutes, 80 DEG C of drying 10h, obtain the integrated negative pole of modified metal oxide-metal in an oven；Described metatitanic acid four Butyl ester (TBOT) is pure to analyze.
The present embodiment has the beneficial effect that：The integrated negative pole of modified metal oxide-metal is washed into using sheet-punching machine Diameter 1.2cm disks (area about 1.13cm-2), it is not necessary to extra conductive agent and binding agent, by it directly as lithium ion GND；Then, lithium metal is as to electrode and reference electrode, and using Celgard barrier films and has dissolved EC/DMC/DEC, 1:1:1vol% 1M LiPF6As electrolyte, button cell is assembled in argon gas atmosphere glove box,
Reference picture 1, it can be seen that：Fig. 1 a-d SEM (SEM) image shown after laser ablation, Copper foil surface forms a large amount of a diameter of several microns cotton shape structures；With the increase of multiplication factor, it can be seen that these Structure is made up of the cluster of the nanoscale similar to cotton structure.This is can be clearly seen that from Fig. 1 e-g TEM image Typical nanometer cotton shape structure is planted, and can be seen that this nanometer cotton shape structure contains substantial amounts of diameter by Fig. 1 g About 5nm nano particle.Wherein, Fig. 1 f are the high resolution transmission electron microscopy (HRTEM) of CuO nanostructured lattice fringes Photo, the distance between two crystal faces areCorresponding to (002) face of monoclinic phase CuO structures.Fig. 1 h constituency electricity Sub- diffraction (SAED) photo display, which goes out prepared CuO samples, has polycrystalline diffraction ring, its correspond respectively to CuO (111),(022) andFace, thus proves the presence of CuO nanocrystals.
Reference picture 2, it can be seen that：Obtained XRD is tested to cotton shape CuO-Cu integrated electrodes oxide side using XRD In spectrum, 43.3 °, 50.5 ° and 74.2 ° of three strong diffraction maximum corresponds respectively to (111), (200) and (220) face of copper foil, Weak diffraction maximum corresponds to monoclinic phase CuO's at the three of 35.5 °, 38.7 ° and 61.5 °(111)/(200),Face (JCPDS No.48-1548), it was demonstrated that CuO is covered in the surface of Cu paper tinsels.
Reference picture 3, it can be seen that：Electro-chemical test is carried out to cotton shape CuO-Cu integrated electrodes and has obtained outstanding electricity Chemical property.Fig. 3 a illustrate the high rate performance of the cotton shape CuO-Cu integrated electrodes under different current densities. 0.3A g-1Circulation 10 is enclosed under current density, and reversible capacity has reached 567.5mA h g-1；Increase to 0.5 with current density, 0.8th, 1.5 and 2.0A g-1When, capacity is decreased to 528.5,473.5,388.9 and 330.4mA h g respectively-1.But with electric current Density is reduced to 0.3A g-1Afterwards, 586.1mA h g can be obtained again-1High discharge capacity, it was demonstrated that CuO-Cu integration electricity Pole possesses outstanding high rate performance.Fig. 3 b show cotton shape CuO-Cu integrated electrodes in 0.8A g-1With 1.5A g-1Electricity The discharge capacity of second of circulation is 484mA h g under current density-1With 453.3mA h g-1.After 500 times circulate, still protect 528.9mA h g are held-1(0.8A g—1) and 393.4mA h g-1(1.5A g-1) reversible capacity.In Fig. 3 c, in 1.5A g-1 Circulated under current density after 800 times, the discharge capacity of cotton shape CuO-Cu integrated electrodes has remained at 393.6mA h g-1, it was demonstrated that oxidation-reduction process that the resistance that the electrode can be remarkably in extended-life lithium ion battery is quickly carried out and holding Stable circulation.
Reference picture 4, it can be seen that：Contrast without laser ablation sample (left side), copper foil surface change it is coarse and Color burn (right side), reason is the formation of copper foil surface CuO particles and causes copper foil surface due to surface roughness exacerbation Irreflexive increase causes surface color to deepen.
Carry out charge discharge performance test：In 1.5A g-1High current density under, circulation 800 times after, coulombic efficiency More than 99% is remained at, the discharge capacity of the 800th circulation is 393.6mAh g-1, compared to the capacity of second of circulation 453.3mAh g-1, its capability retention is 87%.
Embodiment two
A kind of laser ablation oxidation in-situ preparation method of the integrated negative pole of lithium ion battery, comprises the following steps：
1) tinsel is cleaned by ultrasonic 30 minutes respectively using acetone and deionized water, the impurity on surface is removed；Gold Category paillon foil is iron, and purity reaches more than 99.99%, 100 μm of thickness；
2) under room temperature and air atmosphere, irradiation tinsel, optical maser wavelength are scanned respectively using ps pulsed laser and ns pulsed laser 532nm, pulse frequency 20000Hz, pulsewidth 10ns, single pulse energy 1.5 × 10-4J, laser scanning surface speed 15mm s-1, laser Perpendicular to tinsel, the integrated negative pole of metal oxide-metal is obtained；
3) the integrated negative pole of metal oxide-metal is put into 90 DEG C of dry 8h in vacuum drying chamber；
4) by the integrated negative pole of dried metal oxide-metal in the mixed of butyl titanate (TBOT) and absolute ethyl alcohol Close in solution and soak 5 seconds, the volume ratio 1 of butyl titanate (TBOT) and absolute ethyl alcohol:100；Then hydrolyze naturally in atmosphere 10 minutes, 90 DEG C of drying 6h, obtained the integrated negative pole of modified metal oxide-metal in an oven；The described fourth of metatitanic acid four Ester (TBOT) is pure to analyze.
The beneficial effect of the present embodiment：The integrated negative pole of modified metal oxide-metal is washed into directly using sheet-punching machine Footpath 1.2cm disks (area about 1.13cm-2), it is not necessary to extra conductive agent and binding agent, by it directly as lithium-ion electric Pond negative pole.Then, lithium metal is as to electrode and reference electrode, and using Celgard barrier films and has dissolved EC/DMC/DEC, 1: 1:1vol% 1M LiPF6As electrolyte, button cell is assembled into argon gas atmosphere glove box.
Carry out charge discharge performance test：In 0.24mA cm-2Under current density, after circulating 300 times, still present Go out stable discharge capacity 0.25mAh cm-2；In 0.36mA cm-2After being circulated 300 times under current density, discharge capacity is 0.18mAh cm-2, coulombic efficiency is all higher than 99%.
Embodiment three
A kind of laser ablation oxidation in-situ preparation method of the integrated negative pole of lithium ion battery, comprises the following steps：
1) tinsel is cleaned by ultrasonic 30 minutes respectively using alcohol and deionized water, the impurity on surface is removed；Gold Category paillon foil is nickel, and purity reaches more than 99.99%, 100 μm of thickness；
2) under room temperature and air atmosphere, irradiation tinsel, optical maser wavelength are scanned respectively using ps pulsed laser and ns pulsed laser 532nm, pulse frequency 10000Hz, pulsewidth 10ns, single pulse energy 1.5 × 10-4J, laser scanning surface speed 20mm s-1, laser Perpendicular to tinsel, the integrated negative pole of metal oxide-metal is obtained；
3) the integrated negative pole of metal oxide-metal is put into 80 DEG C of dry 10h in vacuum drying chamber；
4) by the integrated negative pole of dried metal oxide-metal in the mixed of butyl titanate (TBOT) and absolute ethyl alcohol Close in solution and soak 10 seconds, the volume ratio 1 of butyl titanate (TBOT) and absolute ethyl alcohol:500；Then hydrolyze naturally in atmosphere 3 minutes, 60 DEG C of drying 12h, obtained the integrated negative pole of modified metal oxide-metal in an oven；The described fourth of metatitanic acid four Ester (TBOT) is pure to analyze.
The beneficial effect of the present embodiment：
Using sheet-punching machine the integrated negative pole of modified metal oxide-metal is washed into diameter 1.2cm disks, and (area is about 1.13cm-2), it is not necessary to extra conductive agent and binding agent, by it directly as negative electrode of lithium ion battery；Then, lithium metal is made For to electrode and reference electrode, and using Celgard barrier films and EC/DMC/DEC, 1 are dissolved:1:1vol% 1M LiPF6 It is used as electrolyte.Button cell is assembled into argon gas atmosphere glove box.
Carry out charge discharge performance test：In 0.24mA cm-2Under current density, after circulating 400 times, discharge capacity Reach 0.18mAh cm-2；In 0.36mA cm-2Under current density, after circulating 400 times, discharge capacity reaches 0.175mAh cm-2, Coulombic efficiency is all higher than 99%.
Example IV
A kind of laser ablation oxidation in-situ preparation method of the integrated negative pole of lithium ion battery, comprises the following steps：
1) tinsel is cleaned by ultrasonic 30 minutes respectively using acetone and deionized water, the impurity on surface is removed；Gold Category paillon foil is tungsten, and purity reaches more than 99.99%, and length × width x thickness is：10mm×10mm×1mm；
2) under room temperature and air atmosphere, irradiation tinsel, optical maser wavelength are scanned respectively using ps pulsed laser and ns pulsed laser 532nm, pulse frequency 10000Hz, pulsewidth 10ns, single pulse energy 1.5 × 10-4J, laser scanning surface speed 10mm s-1, laser Perpendicular to tinsel, the integrated negative pole of metal oxide-metal is obtained；
3) the integrated negative pole of metal oxide-metal is put into 70 DEG C of dry 12h in vacuum drying chamber；
4) by the integrated negative pole of dried metal oxide-metal in the mixed of butyl titanate (TBOT) and absolute ethyl alcohol Close in solution and soak 30 seconds, the volume ratio 1 of butyl titanate (TBOT) and absolute ethyl alcohol:20；Then 2 are hydrolyzed naturally in atmosphere Minute, 80 DEG C of drying 8h, obtain the integrated negative pole of modified metal oxide-metal in an oven；Described butyl titanate (TBOT) it is pure to analyze.
The present embodiment has the beneficial effect that：
Modified TiO2The WO of cladding3- W integration negative poles, lithium metal is used as to electrode and reference electrode Celgard barrier films and EC/DMC/DEC, 1 are dissolved:1:1vol% 1M LiPF6It is used as electrolyte.In argon gas atmosphere gloves Button cell is assembled into case, charge discharge performance test is carried out.In 0.20mA cm-2Circulated 200 times under current density Afterwards, discharge capacity reaches 0.60mAh cm-2, coulombic efficiency is all higher than 99%.

Claims (6)

1. the laser ablation oxidation in-situ preparation method of the integrated negative pole of a kind of lithium ion battery, it is characterised in that including following Step：
1) tinsel is cleaned by ultrasonic 30 minutes respectively using alcohol or acetone and deionized water, the impurity on surface is removed； Tinsel is copper, iron, nickel, tungsten or molybdenum, and purity reaches more than 99.99%；
2) under room temperature and air atmosphere, irradiation tinsel is scanned respectively using ps pulsed laser and ns pulsed laser, optical maser wavelength 532nm, 1000~30000Hz of pulse frequency, 1~100ns of pulsewidth, single pulse energy 0.1~10 × 10-4J, laser scanning surface speed 5~ 300mm s-1, laser vertical obtains the integrated negative pole of metal oxide-metal in tinsel；
3) the integrated negative pole of metal oxide-metal is put into 60~90 DEG C of dry 6~12h in vacuum drying chamber；
4) it is the integrated negative pole of dried metal oxide-metal is molten in the mixing of butyl titanate (TBOT) and absolute ethyl alcohol Soaked 1~60 second in liquid, the volume ratio 1 of butyl titanate (TBOT) and absolute ethyl alcohol:5~1:5000；Then in atmosphere certainly So hydrolysis 1~10 minute, dries 6-12h for 60-90 DEG C in an oven, obtains the integrated negative pole of modified metal oxide-metal； Described butyl titanate (TBOT) is pure to analyze.
2. a kind of integrated negative pole of the lithium ion battery prepared according to claim 1, it is characterised in that：Modified metal is aoxidized Thing-metal-integral negative pole is washed into diameter 1.2cm disks using sheet-punching machine, by it directly as negative electrode of lithium ion battery；Then, Lithium metal using Celgard barrier films and has dissolved EC/DMC/DEC, 1 as to electrode and reference electrode:1:1vol% 1M LiPF6As electrolyte, button cell is assembled in argon gas atmosphere glove box.
3. a kind of laser ablation oxidation in-situ preparation method of the integrated negative pole of lithium ion battery according to claim 1, It is characterised in that it includes following steps：
1) tinsel is cleaned by ultrasonic 30 minutes respectively using alcohol and deionized water, the impurity on surface is removed；Metal foil Piece is copper, and purity reaches more than 99.99%, 100 μm of thickness；
2) under room temperature and air atmosphere, irradiation tinsel is scanned respectively using ps pulsed laser and ns pulsed laser, optical maser wavelength 532nm, Pulse frequency 30000Hz, pulsewidth 10ns, single pulse energy 1.5 × 10-4J, laser scanning surface speed 25mm s-1, laser vertical in Tinsel, obtains the integrated negative pole of metal oxide-metal；
3) the integrated negative pole of metal oxide-metal is put into 60 DEG C of dry 6h in vacuum drying chamber；
4) it is the integrated negative pole of dried metal oxide-metal is molten in the mixing of butyl titanate (TBOT) and absolute ethyl alcohol Soaked 50 seconds in liquid, the volume ratio 1 of butyl titanate (TBOT) and absolute ethyl alcohol:5000；Then 5 points are hydrolyzed naturally in atmosphere Clock, 80 DEG C of drying 10h, obtain the integrated negative pole of modified metal oxide-metal in an oven；Described butyl titanate (TBOT) it is pure to analyze.
4. a kind of laser ablation oxidation in-situ preparation method of the integrated negative pole of lithium ion battery according to claim 1, It is characterised in that it includes following steps：
1) tinsel is cleaned by ultrasonic 30 minutes respectively using acetone and deionized water, the impurity on surface is removed；Metal foil Piece is iron, and purity reaches more than 99.99%, 100 μm of thickness；
2) under room temperature and air atmosphere, irradiation tinsel is scanned respectively using ps pulsed laser and ns pulsed laser, optical maser wavelength 532nm, Pulse frequency 20000Hz, pulsewidth 10ns, single pulse energy 1.5 × 10-4J, laser scanning surface speed 15mm s-1, laser vertical in Tinsel, obtains the integrated negative pole of metal oxide-metal；
3) the integrated negative pole of metal oxide-metal is put into 90 DEG C of dry 8h in vacuum drying chamber；
4) it is the integrated negative pole of dried metal oxide-metal is molten in the mixing of butyl titanate (TBOT) and absolute ethyl alcohol Soaked 5 seconds in liquid, the volume ratio 1 of butyl titanate (TBOT) and absolute ethyl alcohol:100；Then 10 points are hydrolyzed naturally in atmosphere Clock, 90 DEG C of drying 6h, obtain the integrated negative pole of modified metal oxide-metal in an oven；Described butyl titanate (TBOT) it is pure to analyze.
5. a kind of laser ablation oxidation in-situ preparation method of the integrated negative pole of lithium ion battery according to claim 1, It is characterised in that it includes following steps：
1) tinsel is cleaned by ultrasonic 30 minutes respectively using alcohol and deionized water, the impurity on surface is removed；Metal foil Piece is nickel, and purity reaches more than 99.99%, 100 μm of thickness；
2) under room temperature and air atmosphere, irradiation tinsel is scanned respectively using ps pulsed laser and ns pulsed laser, optical maser wavelength 532nm, Pulse frequency 10000Hz, pulsewidth 10ns, single pulse energy 1.5 × 10-4J, laser scanning surface speed 20mm s-1, laser vertical in Tinsel, obtains the integrated negative pole of metal oxide-metal；
3) the integrated negative pole of metal oxide-metal is put into 80 DEG C of dry 10h in vacuum drying chamber；
4) it is the integrated negative pole of dried metal oxide-metal is molten in the mixing of butyl titanate (TBOT) and absolute ethyl alcohol Soaked 10 seconds in liquid, the volume ratio 1 of butyl titanate (TBOT) and absolute ethyl alcohol:500；Then 3 points are hydrolyzed naturally in atmosphere Clock, 60 DEG C of drying 12h, obtain the integrated negative pole of modified metal oxide-metal in an oven；Described butyl titanate (TBOT) it is pure to analyze.
6. a kind of laser ablation oxidation in-situ preparation method of the integrated negative pole of lithium ion battery according to claim 1, It is characterised in that it includes following steps：
1) tinsel is cleaned by ultrasonic 30 minutes respectively using acetone and deionized water, the impurity on surface is removed；Metal foil Piece is tungsten, and purity reaches more than 99.99%, and length × width x thickness is：10mm×10mm×1mm；
2) under room temperature and air atmosphere, irradiation tinsel is scanned respectively using ps pulsed laser and ns pulsed laser, optical maser wavelength 532nm, Pulse frequency 10000Hz, pulsewidth 10ns, single pulse energy 1.5 × 10-4J, laser scanning surface speed 10mm s-1, laser vertical in Tinsel, obtains the integrated negative pole of metal oxide-metal；
3) the integrated negative pole of metal oxide-metal is put into 70 DEG C of dry 12h in vacuum drying chamber；
4) it is the integrated negative pole of dried metal oxide-metal is molten in the mixing of butyl titanate (TBOT) and absolute ethyl alcohol Soaked 30 seconds in liquid, the volume ratio 1 of butyl titanate (TBOT) and absolute ethyl alcohol:20；Then 2 points are hydrolyzed naturally in atmosphere Clock, 80 DEG C of drying 8h, obtain the integrated negative pole of modified metal oxide-metal in an oven；Described butyl titanate (TBOT) it is pure to analyze.
CN201710375337.4A 2017-05-24 2017-05-24 A kind of laser ablation oxidation in-situ preparation method of lithium ion battery integration cathode Active CN107221637B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710375337.4A CN107221637B (en) 2017-05-24 2017-05-24 A kind of laser ablation oxidation in-situ preparation method of lithium ion battery integration cathode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710375337.4A CN107221637B (en) 2017-05-24 2017-05-24 A kind of laser ablation oxidation in-situ preparation method of lithium ion battery integration cathode

Publications (2)

Publication Number Publication Date
CN107221637A true CN107221637A (en) 2017-09-29
CN107221637B CN107221637B (en) 2019-07-12

Family

ID=59944355

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710375337.4A Active CN107221637B (en) 2017-05-24 2017-05-24 A kind of laser ablation oxidation in-situ preparation method of lithium ion battery integration cathode

Country Status (1)

Country Link
CN (1) CN107221637B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108987858A (en) * 2018-06-19 2018-12-11 南京大学 Lithium air/oxygen battery based on metal collector and preparation method thereof
CN114005963A (en) * 2021-11-02 2022-02-01 北京化工大学 Modification method of graphite negative plate of lithium ion battery
CN114590850A (en) * 2022-03-17 2022-06-07 中国长江三峡集团有限公司 Novel vulcanized positive electrode material for sulfide all-solid-state lithium battery and preparation method thereof
US11984599B2 (en) * 2019-11-27 2024-05-14 GM Global Technology Operations LLC Electrode components with laser induced surface modified current collectors and methods of making the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1154106A (en) * 1997-08-05 1999-02-26 Japan Storage Battery Co Ltd Removing method of active material and manufacture of electrode by using this method
US20080263855A1 (en) * 2007-04-27 2008-10-30 Front Edge Technology, Inc. Thin film battery substrate cutting and fabrication process
CN103199299A (en) * 2012-01-06 2013-07-10 王复民 Lithium ion battery anode protection layer and its manufacturing method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1154106A (en) * 1997-08-05 1999-02-26 Japan Storage Battery Co Ltd Removing method of active material and manufacture of electrode by using this method
US20080263855A1 (en) * 2007-04-27 2008-10-30 Front Edge Technology, Inc. Thin film battery substrate cutting and fabrication process
CN103199299A (en) * 2012-01-06 2013-07-10 王复民 Lithium ion battery anode protection layer and its manufacturing method

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108987858A (en) * 2018-06-19 2018-12-11 南京大学 Lithium air/oxygen battery based on metal collector and preparation method thereof
CN108987858B (en) * 2018-06-19 2020-12-04 南京大学 Lithium air/oxygen battery based on metal current collector and preparation method thereof
US11984599B2 (en) * 2019-11-27 2024-05-14 GM Global Technology Operations LLC Electrode components with laser induced surface modified current collectors and methods of making the same
CN114005963A (en) * 2021-11-02 2022-02-01 北京化工大学 Modification method of graphite negative plate of lithium ion battery
CN114590850A (en) * 2022-03-17 2022-06-07 中国长江三峡集团有限公司 Novel vulcanized positive electrode material for sulfide all-solid-state lithium battery and preparation method thereof
CN114590850B (en) * 2022-03-17 2023-04-18 中国长江三峡集团有限公司 Vulcanized positive electrode material for sulfide all-solid-state lithium battery and preparation method thereof

Also Published As

Publication number Publication date
CN107221637B (en) 2019-07-12

Similar Documents

Publication Publication Date Title
Yu et al. Electrode–electrolyte interfaces in lithium-based batteries
Zou et al. Chromium-modified Li4Ti5O12 with a synergistic effect of bulk doping, surface coating, and size reducing
CN106848328B (en) A kind of negative current collector, battery cathode, battery and preparation method thereof
Pan et al. Flower-like CuO film-electrode for lithium ion batteries and the effect of surface morphology on electrochemical performance
CN107221637B (en) A kind of laser ablation oxidation in-situ preparation method of lithium ion battery integration cathode
CN108448055A (en) Anode material for lithium-ion batteries and preparation method thereof
Huang et al. ZnO microrod arrays grown on copper substrates as anode materials for lithium ion batteries
Liang et al. In situ preparation of a binder-free nano-cotton-like CuO–Cu integrated anode on a current collector by laser ablation oxidation for long cycle life Li-ion batteries
CN108288703B (en) Preparation method and application of graphene-coated fluorine-doped lithium titanate nanowire
CN102208631A (en) Ultra-long single crystal V2O5 nano wire/graphene anode material and preparation method
CN109524649B (en) Sodium-ion battery positive electrode material with coating structure and preparation method and application thereof
CN110304658B (en) Nb for lithium ion battery18W16O93Negative electrode material and preparation method thereof
Chen et al. Superior wide-temperature lithium storage in a porous cobalt vanadate
Liu et al. “Dual‐Engineering” Strategy to Regulate NH4V4O10 as Cathodes for High‐Performance Aqueous Zinc Ion Batteries
CN105914369A (en) Nanoscale carbon coated lithium sulfide composite material, preparation method and application thereof
Chen et al. Lithium, sodium and potassium storage behaviors of Pb3Nb4O13 nanowires for rechargeable batteries
Zhong et al. Design Strategy of High Stability Vertically Aligned RGO@ V2O5 Heterostructure Cathodes for Flexible Quasi-Solid-State Aqueous Zinc-Ion Batteries
CN105161678A (en) Multi-layer composite titanium dioxide nanotube material for lithium battery electrode
CN113571681B (en) Hollow titanium dioxide/nickel/carbon composite material and preparation method and application thereof
CN114243007A (en) Nickel disulfide/carbon nanotube composite electrode material and preparation method and application thereof
CN112186166B (en) Molybdenum/cobalt oxide-carbon composite material and preparation method thereof, lithium ion battery negative electrode piece and lithium ion battery
CN107170978A (en) A kind of carbon coating titanium dioxide mesomorphic nano composite material and its application
CN103553129B (en) Application of sodium ion battery cathode material sodium bismuth disulfide nanoparticles
Chen et al. Cu 2 O nanowires as anode materials for Li-ion rechargeable batteries
Cheng et al. Cubic CuCo2O4 microspheres with FeO nanowires link as free-standing anode for high-performance lithium ion batteries

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant