CN111900383B - Doped lithium ion energy storage power battery anode and preparation method thereof - Google Patents
Doped lithium ion energy storage power battery anode and preparation method thereof Download PDFInfo
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- CN111900383B CN111900383B CN202010712091.7A CN202010712091A CN111900383B CN 111900383 B CN111900383 B CN 111900383B CN 202010712091 A CN202010712091 A CN 202010712091A CN 111900383 B CN111900383 B CN 111900383B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- 238000004146 energy storage Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 117
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 101
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 101
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000002019 doping agent Substances 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical class [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052878 cordierite Inorganic materials 0.000 claims description 5
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000000498 cooling water Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000002739 metals Chemical class 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 229910010710 LiFePO Inorganic materials 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- General Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
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- Materials Engineering (AREA)
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Abstract
The invention provides a preparation method of a doped lithium ion energy storage power battery anode, which comprises the following steps: s1, providing a carbon nano tube array framework, wherein the carbon nano tube array framework comprises a plurality of carbon nano tubes closely arranged along the same direction and a carbon connecting layer connected between adjacent carbon nano tubes; s2, according to the molar mass ratio of 1.05-1.2: (1-x): 1.1 to 1.2: 2to 3:x LiOH H is added 2 O、FeC 2 O 4 ·2H 2 O、NH 4 H 2 PO 4 、C 6 H 8 O 7 ·H 2 O and dopants are dissolved in water to form a reaction solution, wherein the concentration of Fe in the reaction solution is 0.2-0.4 mol/L, the dopants are sodium hydroxide or oxide of metals such as Mg, co, ni and/or Mn, and x is 0.05-0.15; s3, immersing the carbon nano tube array skeleton in the reaction solution, enabling the reaction solution to flow through the carbon nano tube array skeleton, and controlling the reaction temperature to be 145-155 ℃ for reacting for 1-12h to enable LiFe (1‑x) M x PO 4 And M is doped metal and is deposited inside and on the surface of the carbon nanotube array framework.
Description
Technical Field
The invention relates to a doped lithium ion energy storage power battery anode and a preparation method thereof.
Background
The lithium ion power battery has the characteristics of high working voltage, high energy density, low self-discharge rate, recycling and the like, and becomes the most widely used power supply in the field of current mobile equipment.
Currently, the positive electrode of a traditional lithium ion power battery is generally prepared by coating a positive electrode active material on the surface of a current collector such as a copper foil. The contact between the positive electrode active material and a current collector such as copper foil is less tight, so that the interface resistance of the positive electrode active material is higher.
Disclosure of Invention
The invention provides a doped lithium ion energy storage power battery anode and a preparation method thereof, which can effectively solve the problems.
The invention is realized in the following way:
the invention provides a preparation method of a doped lithium ion energy storage power battery anode, which comprises the following steps:
s1, providing a carbon nano tube array framework, wherein the carbon nano tube array framework comprises a plurality of carbon nano tubes closely arranged along the same direction and a carbon connecting layer connected between adjacent carbon nano tubes;
s2, according to the molar mass ratio of 1.05-1.2: (1-x): 1.1 to 1.2: 2to 3:x LiOH H is added 2 O、FeC 2 O 4 ·2H 2 O、NH 4 H 2 PO 4 、C 6 H 8 O 7 ·H 2 O and dopants are dissolved in water to form a reaction solution, wherein the concentration of Fe in the reaction solution is 0.2-0.4 mol/L, the dopants are sodium hydroxide or oxide of metals such as Mg, co, ni and/or Mn, and x is 0.05-0.15;
s3, immersing the carbon nano tube array framework into the reaction solution to dissolve the reactionThe liquid flows through the carbon nano tube array skeleton and reacts for 1 to 12 hours at the reaction temperature of 145 to 155 ℃ to lead LiFe (1-x) M x PO 4 And M is doped metal and is deposited inside and on the surface of the carbon nanotube array framework.
The invention further provides a doped lithium ion energy storage power battery anode obtained by the method.
The beneficial effects of the invention are as follows: by mixing said LiFe (1-x) M x PO 4 The active material is deposited inside and on the surface of the carbon nanotube array framework, so that the contact area and the contact force between the active material and the carbon nanotube array framework can be increased, an ion channel is increased, and the contact resistance between the active material and the carbon nanotube array framework (serving as a current collector) is reduced; in addition, the invention provides the method for preparing the iron site doped nano lithium iron phosphate by taking the Mg, mn, co and/or Ni compounds as doping raw materials, so that the basic battery performance of the lithium iron phosphate LiFePO4 cathode material is improved, and the lithium iron phosphate cathode material has higher charge-discharge capacity and good battery cycle performance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some examples of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flowchart of a method for preparing an anode of a lithium ion energy storage power battery according to an embodiment of the invention.
Fig. 2 is a schematic structural diagram of a reaction furnace used in the method for preparing the positive electrode of the lithium ion energy storage power battery according to the embodiment of the invention.
Fig. 3 is a schematic structural diagram of a reaction kettle used in the preparation method of the positive electrode of the lithium ion energy storage power battery provided by the embodiment of the invention.
Fig. 4 is a flowchart of a method for preparing an anode of a lithium ion energy storage power battery according to another embodiment of the invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention. Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention.
In the description of the present invention, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
Referring to fig. 1, an embodiment of the present invention provides a method for preparing an anode of a lithium ion energy storage power battery, including the following steps:
s1, providing a carbon nano tube array framework, wherein the carbon nano tube array framework comprises a plurality of carbon nano tubes closely arranged along the same direction and a carbon connecting layer connected between adjacent carbon nano tubes;
s2, according to the molar mass ratio of 1.05-1.2: 1:1.1 to 1.2: 2to 3 LiOH H is added 2 O、FeC 2 O 4 ·2H 2 O、NH 4 H 2 PO 4 C 6 H 8 O 7 ·H 2 O is dissolved inForming a reaction solution in water, wherein the concentration of Fe in the reaction solution is 0.2-0.4 mol/L;
s3, immersing the carbon nano tube array skeleton in the reaction solution, enabling the reaction solution to flow through the carbon nano tube array skeleton, and controlling the reaction temperature to be 145-155 ℃ for reacting for 1-12h to enable LiFePO 4 And the carbon nano tube array is deposited inside and on the surface of the carbon nano tube array framework.
In step S1, the preparation method of the carbon nanotube array skeleton includes the following steps:
s11, fixing the carbon nano tube array on a porous substrate;
and S12, under the condition of protective atmosphere, ethylene gas flows from the top end of the carbon nano tube array to the porous substrate at the bottom end, the reaction temperature is controlled to be 800-850 ℃, and the reaction time is controlled to be 20-60 minutes, so that the carbon nano tube array skeleton is formed.
In step S11, the method for preparing the carbon nanotube array may adopt a chemical vapor deposition method.
Specific: (a) providing a flat silicon substrate; (b) Uniformly forming an iron (Fe) catalyst layer on the surface of the substrate; (c) Annealing the substrate with the catalyst layer in the air at 700-900 ℃ for about 30-90 minutes; (d) Placing the treated substrate in a low-pressure reaction furnace, heating to 700-710 ℃ in a nitrogen environment at the atmospheric pressure of about 0.2torr, then introducing acetylene to react for about 20-30 minutes, and growing to obtain a carbon nanotube array; (e) And scraping the carbon nanotube array from the substrate by adopting a blade or other tools to obtain the carbon nanotube array. The carbon nanotube array is a pure carbon nanotube array formed by a plurality of carbon nanotubes which are parallel to each other and are grown perpendicular to a substrate. The height of the carbon nanotubes is 50-500 micrometers, and the distance between the carbon nanotubes is 10-500 nanometers.
The carbon nanotube array is tiled on the cordierite honeycomb substrate after the carbon nanotube array is scraped off the substrate. The cordierite honeycomb substrate has a uniformly distributed porous structure that allows for a slow and uniform flow of gas therethrough.
Referring to fig. 2, in step S12, a cordierite honeycomb substrate 12 with a carbon nanotube array 13 laid thereon may be placed on a bottom suction reactor for reaction. Specifically, the reaction furnace includes: an upper cover 10 and a reaction chamber 11 screw-fitted with the upper cover 10; the bottom of the reaction chamber 11 is provided with a bottom suction type exhaust funnel 14, and the exhaust funnel 14 is provided with a vacuum pump 15. The upper cover 10 comprises a first air inlet 101, a second air inlet 102 and a third air inlet 103 which is uniformly distributed on the lower surface and has a diameter of 1-5 mm, the first air inlet 101 is communicated with the third air inlet 103, and the second air inlet 102 is also communicated with the third air inlet 103. The first gas inlet 101 is used for introducing protective atmosphere, and the second gas inlet 102 is used for introducing ethylene gas. The side wall of the reaction chamber 11 is provided with a plurality of resistance wires 111, and the bottom of the reaction chamber 11 is provided with a plurality of uniformly distributed exhaust holes 112. The exhaust port 141 is provided at the bottom of the exhaust pipe 14, and the pressure sensor 142 is provided near the exhaust port 141, so that the pressure sensor 142 is prevented from being damaged by high temperature by providing the pressure sensor 142 in the exhaust port 141 instead of the reaction chamber 11. The side wall of the exhaust stack 14 is further provided with a cooling line 143, which cooling line 143 is used for the gas inside the cooler. The bottom of the reaction chamber 11 is tightly matched with the exhaust funnel 14 in a threaded manner, and an annular sealing ring 113 is further arranged at the joint between the reaction chamber 11 and the exhaust funnel 14.
The atmospheric pressure is about 0.5 to 1.0torr, the temperature is heated to 800 to 850 ℃ in the nitrogen environment, then the nitrogen is closed and ethylene is introduced to react for about 20 minutes to 60 minutes (in the reaction process, the atmospheric pressure is kept about 0.5 to 1.0torr by controlling the flow of ethylene gas and a vacuum pump), so that a carbon connecting layer is connected between adjacent carbon nanotubes to form a framework between the fixed carbon nanotubes. It is understood that the thicker the carbon connecting layer can be formed on the surface of each carbon nanotube when the reaction time is longer, the greater the skeleton strength is, but the thicker the carbon connecting layer is, the more easily the gaps between the carbon nanotubes are blocked. When the reaction time is short, the connection strength between the carbon nanotubes is low, and the carbon nanotubes are easily expanded by the expansion of silicon to be damaged. Therefore, the reaction time is preferably about 30 minutes. The carbon connecting layer has a thickness of 10 nm to 20 nm. In addition, the thickness of the carbon connecting layer can also be controlled by controlling the concentration of the ethylene gas.
In step S2, the molar mass ratio 1.1 is preferably: 1:1.1:2.5 LiOH H addition 2 O、FeC 2 O 4 ·2H 2 O、NH 4 H 2 PO 4 C 6 H 8 O 7 ·H 2 O was dissolved in water to form a reaction solution, and the concentration of Fe in the reaction solution was about 0.3mol/L.
Referring to fig. 3, in step S3, a reaction apparatus is further provided. The reaction apparatus includes:
a top cover (20);
the reaction kettle (21) is in threaded fit with the top cover (20), comprises a pressurizing air inlet (214) arranged at the top, a heating wire (211) arranged at the bottom in a surrounding manner, an ultrasonic generator (215) arranged on the side wall, and a plurality of through holes (212) uniformly distributed are formed in the bottom of the reaction kettle (21);
and the bottom suction type liquid draining cylinder (22) is arranged at the bottom of the reaction kettle (21) and communicated with the through hole (212).
The bottom suction drain (22) further includes a cooling water circuit (222). The bottom of the reaction kettle (21) is tightly matched with the liquid discharge cylinder (22) in a threaded mode, and an annular sealing ring 213 is further arranged at the joint part between the reaction kettle (21) and the liquid discharge cylinder (22).
In step S3, further comprising:
s31, fixing the carbon nano tube array framework at the bottom of the reaction kettle (21), enabling the carbon nano tube array framework to cover the through holes (212), wherein the diameter of each through hole (212) is 1-10 microns, and the through holes are uniformly distributed at intervals, so that the flow rate of the reaction solution can be controlled;
s32, pouring the reaction solution into the bottom of a reaction kettle (21) and immersing the carbon nanotube array skeleton, and then covering the top cover (20);
s33, pressurizing through the pressurizing air inlet (214) and controlling the ultrasonic generator (215) to work, wherein the pressure is 0.2-0.5 MPa, and the power of the ultrasonic generator (215) can be 100-500W;
s34, opening the heating wire (211) to perform heating reaction, wherein the heating temperature is 145-155 ℃.
As a further improvement, after step S34, further comprising:
and S35, ending the reaction when the reaction solution cannot flow out. It can be appreciated that LiFePO is illustrated when the reaction solution cannot flow out 4 And the reaction solution is deposited inside and on the surface of the carbon nano tube array framework, so that pores in the carbon nano tube array framework are blocked, and the reaction solution cannot flow through the carbon nano tube array framework.
As a further improvement, in step S33, further comprising:
s331, opening the cooling water channel (222) to cool down, and preventing the reaction solution from reacting in the bottom suction type liquid discharge cylinder (22).
The invention further provides a lithium ion energy storage power battery anode, which is obtained by the method.
The positive electrode of the lithium ion energy storage power battery is a lamellar structure with the thickness of about 80-550 microns, a plurality of closely arranged carbon nanotubes are arranged along the surface vertical to the lamellar structure, a carbon connecting layer for connecting the carbon nanotubes is arranged between the carbon nanotubes to form a carbon nanotube array skeleton and nano LiFePO 4 Filling between adjacent carbon nanotubes in the carbon nanotube array skeleton and partially covering the surface of the carbon nanotube array skeleton. LiFePO in positive electrode of lithium ion energy storage power battery 4 The mass ratio of the carbon nano tube to the carbon nano tube is 1:1.5-1:2. LiFePO in the positive electrode front (upward side during reaction) of the lithium ion energy storage power battery 4 The thickness of (2) is 30-100 micrometers.
Example 1:
scraping the carbon nano tube array from the substrate, spreading the carbon nano tube array on the cordierite honeycomb substrate, and putting the substrate into a reaction furnaceAnd (3) controlling the atmospheric pressure to be about 0.8torr, heating to 830 ℃ in a nitrogen environment, closing nitrogen, introducing ethylene, and reacting for about 30 minutes (in the reaction process, the atmospheric pressure is kept to be about 0.8torr by controlling the flow of ethylene gas and a vacuum pump), so that a carbon connecting layer is connected between adjacent carbon nano tubes to form a framework between the fixed carbon nano tubes. According to the molar mass ratio of 1.1:1:1.1:2.5 LiOH H addition 2 O、FeC 2 O 4 ·2H 2 O、NH 4 H 2 PO 4 C 6 H 8 O 7 ·H 2 O was dissolved in water to form a reaction solution, and the concentration of Fe in the reaction solution was about 0.3mol/L. Fixing the carbon nano tube array framework at the bottom of the reaction kettle, and enabling the carbon nano tube array framework to cover the through holes; pouring the reaction solution into the bottom of a reaction kettle and immersing the carbon nanotube array skeleton; pressurizing and controlling the ultrasonic generator to work, wherein the pressure is 0.4MPa, and the power of the ultrasonic generator is 400W (40 KHZ); and opening the heating wire to perform heating reaction, wherein the heating temperature is 150 ℃, and reacting for 3 hours to obtain the anode of the lithium ion energy storage power battery.
Comparative example 1: substantially the same as in example 1, except that the carbon nanotube array was not subjected to the curing treatment of the carbon connecting layer.
Test example:
the four-probe surface resistance measuring instrument is used for respectively measuring the surface resistance of the positive and negative sides of the lithium ion energy storage power battery, wherein in the embodiment, the surface resistance of the positive side (upward side during reaction) of the positive electrode of the lithium ion energy storage power battery is 61.32+/-8.51 ohm/cm 2 The surface resistance of the back surface (downward surface during reaction) of the positive electrode of the lithium ion energy storage power battery is (0.96+/-0.27). Times.10 -2 Ω/cm 2 . In the comparative example, the positive electrode front side (upward side during reaction) of the lithium ion energy storage power cell had a surface resistance of 5.76.+ -. 1.85×10 2 Ω/cm 2 The surface resistance of the reverse side (downward side during reaction) of the positive electrode of the lithium ion energy storage power battery is 18.16+/-4.56 ohm/cm 2 . Therefore, the positive electrode of the lithium ion energy storage power battery adopts the carbonThe nanotube array skeleton is used as the positive current collector, so that the surface resistance of the positive electrode of the lithium ion energy storage power battery is greatly reduced. In addition, the carbon connecting layer structure also greatly reduces the transverse interface resistance between the carbon nanotubes.
Referring to fig. 4, an embodiment of the present invention provides a method for preparing an anode of a lithium ion energy storage power battery, including the following steps:
s1', providing a carbon nano tube array framework, wherein the carbon nano tube array framework comprises a plurality of carbon nano tubes closely arranged along the same direction and a carbon connecting layer connected between adjacent carbon nano tubes;
s2', wherein the molar mass ratio is 1.05-1.2: (1-x): 1.1 to 1.2: 2to 3:x LiOH H is added 2 O、FeC 2 O 4 ·2H 2 O、NH 4 H 2 PO 4 、C 6 H 8 O 7 ·H 2 O and dopants are dissolved in water to form a reaction solution, wherein the concentration of Fe in the reaction solution is 0.2-0.4 mol/L, the dopants are sodium hydroxide or oxide of metals such as Mg, co, ni and/or Mn, and x is 0.05-0.15;
s3', immersing the carbon nano tube array skeleton in the reaction solution, enabling the reaction solution to flow through the carbon nano tube array skeleton, and controlling the reaction temperature to be 145-155 ℃ for reacting for 1-12h to enable LiFe (1-x) M x PO 4 And M is doped metal and is deposited inside and on the surface of the carbon nanotube array framework.
Wherein steps S1 'to S3' are substantially identical to steps S1 to S3, except that dopant metal ions are added. In one embodiment, the dopant is MgO and the doping amount x is 0.1. The kind and the number of the dopants are not limited, and the dopants can be doped according to practical requirements.
The invention further provides a doped lithium ion energy storage power battery anode, which is obtained by the method.
The anode of the doped lithium ion energy storage power battery is of a lamellar structure with the thickness of about 80-550 microns and is vertical to the anodeThe surface of the lamellar structure is provided with a plurality of closely arranged carbon nanotubes, and carbon connecting layers for connecting the carbon nanotubes are arranged among the carbon nanotubes to form a carbon nanotube array skeleton and nano LiFe (1-x) M x PO 4 Filling between adjacent carbon nanotubes in the carbon nanotube array skeleton and partially covering the surface of the carbon nanotube array skeleton. LiFe in the positive electrode of the lithium ion energy storage power battery (1-x) M x PO 4 The mass ratio of the carbon nano tube to the carbon nano tube is 1:1.5-1:2. LiFe in the positive electrode front (upward face during reaction) of the lithium ion energy storage power battery (1-x) M x PO 4 The thickness of (2) is 30-100 micrometers.
According to the invention, the Mg, mn, co and/or Ni compounds are used as doping raw materials to prepare the iron-site-doped nano lithium iron phosphate, so that the basic battery performance of the lithium iron phosphate LiFePO4 positive electrode material is improved, and the lithium iron phosphate positive electrode material has higher charge-discharge capacity and good battery cycle performance.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, and various modifications and variations may be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The preparation method of the doped lithium ion energy storage power battery anode is characterized by comprising the following steps of:
s1, providing a carbon nano tube array framework, wherein the carbon nano tube array framework comprises a plurality of carbon nano tubes closely arranged along the same direction and a carbon connecting layer connected between adjacent carbon nano tubes, and in the step S1, the preparation method of the carbon nano tube array framework comprises the following steps: s11, fixing the carbon nano tube array on a porous substrate; s12, under the condition of protective atmosphere, enabling ethylene gas to flow from the top end of the carbon nano tube array to the bottom end of the porous substrate, controlling the reaction temperature to be 800-850 ℃ and the reaction time to be 20-60 minutes, and forming a carbon nano tube array skeleton on the porous substrate; the thickness of the carbon connecting layer is 10 nanometers to 20 nanometers;
s2, according to the molar mass ratio of 1.05-1.2: (1-x): 1.1 to 1.2: 2-3:x LiOH.H is added 2 O、 FeC 2 O 4 ·2H 2 O、NH 4 H 2 PO 4 、C 6 H 8 O 7 ·H 2 O and a dopant are dissolved in water to form a reaction solution, wherein the concentration of Fe in the reaction solution is 0.2-0.4 mol/L, the dopant is sodium hydroxide or oxide of Mg, co, ni and/or Mn metal, and x is 0.05-0.15;
s3, immersing the carbon nano tube array skeleton in the reaction solution, enabling the reaction solution to flow through the carbon nano tube array skeleton, and controlling the reaction temperature to be 145-155 ℃ for reacting for 1-12h to enable LiFe （1-x） M x PO 4 And M is doped metal and is deposited inside and on the surface of the carbon nanotube array framework.
2. The method of preparing a doped lithium ion energy storage power cell positive electrode according to claim 1, wherein in step S11, the porous substrate is a cordierite honeycomb substrate.
3. The method of claim 1, wherein in step S3, a reaction device is further provided, comprising:
a top cover (20);
the reaction kettle (21) is in threaded fit with the top cover (20), comprises a pressurizing air inlet (214) arranged at the top, a heating wire (211) arranged at the bottom in a surrounding manner, an ultrasonic generator (215) arranged on the side wall, and a plurality of through holes (212) uniformly distributed are formed in the bottom of the reaction kettle (21);
and the bottom suction type liquid draining cylinder (22) is arranged at the bottom of the reaction kettle (21) and communicated with the through hole (212).
4. The method of preparing a doped lithium-ion energy storage power cell positive electrode according to claim 3, further comprising, in step S3:
s31, fixing the carbon nano tube array framework at the bottom of the reaction kettle (21), and enabling the carbon nano tube array framework to cover the through holes (212);
s32, pouring the reaction solution into the bottom of a reaction kettle (21) and immersing the carbon nanotube array skeleton, and then covering the top cover (20);
s33, pressurizing through the pressurizing air inlet (214) and controlling the ultrasonic generator (215) to work;
s34, opening the heating wire (211) to perform heating reaction, wherein the heating temperature is 145-155 ℃.
5. The method of manufacturing a doped lithium ion energy storage power battery positive electrode according to claim 4, wherein the bottom suction drain (22) further comprises a cooling water path (222), and in step S33, further comprises:
s331, opening the cooling water channel (222) to cool down, and preventing the reaction solution from reacting in the bottom suction type liquid discharge cylinder (22).
6. A doped lithium ion energy storage power cell positive electrode, characterized in that it is obtained by a method according to any one of claims 1-5.
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