CN107706384A - A kind of lithium battery load porous carbon negative pole material of nickel oxide bio-based N doping - Google Patents

A kind of lithium battery load porous carbon negative pole material of nickel oxide bio-based N doping Download PDF

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Publication number
CN107706384A
CN107706384A CN201710893504.4A CN201710893504A CN107706384A CN 107706384 A CN107706384 A CN 107706384A CN 201710893504 A CN201710893504 A CN 201710893504A CN 107706384 A CN107706384 A CN 107706384A
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China
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carbon
porous carbon
doping
nickel oxide
negative pole
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CN201710893504.4A
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Inventor
费本华
张波
陈秀芳
钟明强
赵正平
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Zhejiang University of Technology ZJUT
International Center for Bamboo and Rattan
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Zhejiang University of Technology ZJUT
International Center for Bamboo and Rattan
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Priority to CN201710893504.4A priority Critical patent/CN107706384A/en
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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
    • H01M4/362—Composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • 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
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • 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
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

Abstract

A kind of lithium battery load porous carbon negative pole material of nickel oxide bio-based N doping, it is characterised in that described bio-based N doping porous carbon is bamboo carbon, the one or two of bamboo shoots carbon, and the specific surface area of carbon material is 100~3000m2/ g, nitrogen element content are 0.1~10.0wt.%.It is 5~500nm to load NiO nanoparticle particle diameter.NiO nanoparticle is scattered in ultrasound 30 minutes in tetrahydrofuran solvent, after being uniformly dispersed, add porous carbon and continue ultrasound 20 minutes, high speed centrifugation, deionized water is washed, obtain loading nickel oxide bio-based N doping porous carbon after oven drying, as cathode material of lithium ion battery, the button-shaped half-cells of assembling CR2025 simultaneously test its chemical property.In 100mAg‑1Under current density, first charge-discharge circulation specific capacity is up to 1084mAhg‑1, far above the 370mAhg of the carbon material negative pole material commercially used‑1, and still there is 510mAhg after undergoing 50 charge and discharge cycles‑1Specific capacity value, equally far above commercial carbon material negative pole material.Therefore, it can have extensive commercial value and application prospect as the alternative materials of conventional commercial carbon negative electrode material of lithium ion cell.

Description

A kind of lithium battery load porous carbon negative pole material of nickel oxide bio-based N doping
Technical field
The present invention relates to new energy battery material technical field, specifically a kind of lithium battery load nickel oxide bio-based nitrogen Adulterate porous carbon negative pole material.
Background technology
Different from the traditional energy based on fossil energy, with solar energy, geothermal energy, wind energy etc. for representative new energy in work( There is larger randomness with intermittent in rate output, be otherwise known as the intermittent renewable energy.It is above-mentioned renewable in order to realize Grid-connected application, energy stores and the conversion of the energy, growth-promoting is using safe efficient, environment-friendly secondary cell system as label Chemical energy storage technology by academia extensive concern and Innovation Input.Wherein, lithium ion battery is because capacity is big, operating voltage It is high, self discharge is low, it is safe, have extended cycle life, small volume, it is in light weight, than can high, memory-less effect, a not leaded mercury huge sum of money Category etc. activity beneficial, firmly occupy the existing market principal status of public economy, be widely used in Aero-Space, communications and transportation, household electrical appliances, office, The fields such as mobile communication.Currently low (the 372mAhg of commercial li-ion battery embedded type graphite-like carbon negative pole material specific capacity-1), It can not meet in the high-power high-current device requirement such as electric automobile, ship, electric tool.Therefore, Fabrication of High Specific Capacitance of new generation is explored Amount, high-energy-density, the negative material of high circulation life-span and high rate performance have become study hotspot.
Nickel oxide material is up to 1100mAhg because of it-1Theoretical specific capacity, 2600mAhcm-1Volume and capacity ratio, 0.9eV Energy gap, 0-0.4V operating potentials and 250 DEG C of operating temperatures, turn into most promising negative electrode of lithium ion battery material of future generation One of material.In addition, nickel oxide raw material resources deposit enriches, mature preparation process, it is adapted to exploitation to be born for commercial li-ion battery Pole material.Though nickel oxide has many advantages, such as the above as negative material, some inevitable defects itself are still suffered from：1) Nickel oxide is a kind of semi-conducting material, intrinsic resistivity 1.2*105Ω cm, dielectric constant 8.4, electrical conductivity is relatively low；2) filling During discharge cycles, Li+It is constantly embedded and deviate from, thus nickel oxide material Volume Changes produce a system up to 300% Row problem.Such as：Nickel oxide particle crushes or Materials Fracture is so as to destroy electrode structure, conductive contact is deteriorated, causes under capacity Drop.In electrochemistry cyclic process, uneven polarization caused by along the electrochemical reaction in thickness of electrode direction triggers electrode stratiform Rupture and stripping, and then there is conductive network collapse and electrode failure；3)Li+Be concatenated to form during insertion-abjection solid- Electrolyte interface film (SEI), after multiple charge and discharge cycles, SEI thickness increases ultimately result in Si materials and lose electro-chemical activity, make Into capacitance loss.To solve the above problems, improving nickel oxide material negative material performance, prepare C@NiO composite nano materials and make For negative material, on the basis of nickel oxide material height ratio capacity and energy density is ensured, reduce active material cracking or peel off The electrode failure of initiation, suppress SEI and formed, increase electric conductivity, improve charge-discharge performance.In a word, around high-performance lithium Ion battery application demand, further design and preparation load nickel oxide bio-based N doping porous carbon (C@NiO) base nanometer are born Pole material, improve the charge-discharge performance of lithium ion battery negative material, be still that the field there are important scientific issues to be solved.
The content of the invention
It is an object of the present invention to provide a kind of lithium battery load porous carbon negative pole material of nickel oxide bio-based N doping, biology It is raw material that matter porous carbon materials, which take natural bamboo or bamboo shoots, and preparation technology is simple, can large-scale industrial production, be prepared The porous carbon negative pole material of load nickel oxide bio-based N doping there is excellent chemical property.
To realize above-mentioned technical purpose, the present invention is achieved by the following technical solutions：
A kind of lithium battery load porous carbon negative pole material of nickel oxide bio-based N doping, it is characterised in that described biology Base N doping porous carbon is bamboo carbon, the one or two of bamboo shoots carbon, and the specific surface area of carbon material is 100~3000m2/ g, nitrogen member Cellulose content is 0.1~10.0wt.%.
Described load NiO nanoparticle, particle diameter are 5~500nm.
Preparation technology is：NiO nanoparticle is scattered in ultrasound 30 minutes in tetrahydrofuran solvent, waits to be uniformly dispersed Afterwards, add porous carbon and continue ultrasound 20 minutes, high speed centrifugation, deionized water is washed, and obtains loading nickel oxide life after oven drying Thing base N doping porous carbon.
It is button-shaped using CR2025 to load nickel oxide bio-based N doping porous carbon composite electrode storage lithium performance characterization Half-cell, the C@NiO composites of mass fraction 80%, 10% binding agent Kynoar (PVDF), 10% conductive agent acetylene Carbon black is dissolved in 1-METHYLPYRROLIDONE (NMP) and coated on copper foil, vacuum drying, 6MPa, which is compressed, is used as negative pole stand-by, It is lithium piece to electrode, barrier film uses the how empty barrier film of polypropylene-polyethylene-polypropylene, the carbonic acid two of 1M lithium hexafluoro phosphates (LiPF6) Methyl esters (DMC) and ethylene carbonate (EC) by volume 1:1 prepares electrolyte, and encapsulation carries out half-cell test.
Constant current charge-discharge test is carried out to battery using Land CT2001A (Wuhan is blue rich), by recording discharge and recharge The data such as time, voltage, electric current, capacity in journey, characterize the data such as electrode material cycle life and charge and discharge platform.Using Arbin MSTAT4 (U.S. A Bin) carry out cyclic voltammetry (CV) to battery, obtain electrode and specific electrochemical reaction electricity occurs Position, analyzes sample electrochemical reaction process and mechanism, and electrochemical reaction material category is participated in auxiliary checking.Using CHI660D (on Electrochemical impedance test Hai Chenhua) is carried out, to comparative sample charge transfer resistance size.
The present invention has following beneficial effect compared with prior art：The porous carbon raw material of bio-based N doping is natural bamboo Son or bamboo shoots, processing technology is simple, and gained porous carbon materials specific surface area is 100~3000m2/ g, nitrogen element content be 0.1~ 10.0wt.%.(1) compared with commercial carbons negative material, nickel oxide has more height ratio capacity and energy density, operating potential 0- Between 0.4V, lithium ion battery negative material, and rich reserves are suitable as, are easily obtained.(2) porous carbon materials are handed over for height Join network structure, high-specific surface area and be easy to ion to transmit rich in mesoporous.(3) nickel oxide is semi-conducting material, and poorly conductive is more Hole carbon material can be used as excellence conductor, improve electric conductivity.(4) a large amount of N elements are rich in porous carbon materials, carbon atom ∏ is upset and is total to Yoke electron system, there is provided bigger electrochemical surface area and avtive spot, collaboration promote electric charge transfer between carbon atom and hetero atom, Lift carbon layer material conductance and specific capacity.(5) C@NiO composite nano materials preparation technologies are simple, are advantageous to scale application.
Brief description of the drawings
Fig. 1 is bio-based porous carbon materials scanning electron microscope (SEM) photograph of the present invention；
Fig. 2 is load nickel oxide bio-based N doping porous carbon scanning electron microscope (SEM) photograph prepared by embodiment 1；
Fig. 3 is load nickel oxide bio-based N doping porous carbon cathode material lithium ion battery charge and discharge prepared by embodiment 1 Electric cycle performance.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention Content is not limited solely to the following examples.
Embodiment 1：
A kind of lithium battery load porous carbon negative pole material of nickel oxide bio-based N doping, it is characterised in that described biology Base N doping porous carbon is bamboo carbon, and the specific surface area of carbon material is 500m2/ g, nitrogen element content 1.0wt.%.
Described load NiO nanoparticle, particle diameter 50nm.
5g NiO nanoparticles are scattered in ultrasound 30 minutes in tetrahydrofuran solvent, after being uniformly dispersed, added 100g porous carbons continue ultrasound 20 minutes, high speed centrifugation, deionized water washing, obtain loading nickel oxide life after 40 DEG C of oven dryings Thing base N doping porous carbon, assemble battery as lithium ion battery negative material and test its charge-discharge performance.
Embodiment 2：
A kind of lithium battery load porous carbon negative pole material of nickel oxide bio-based N doping, it is characterised in that described biology Base N doping porous carbon is bamboo carbon, and the specific surface area of carbon material is 1000m2/ g, nitrogen element content 3.0wt.%.
Described load NiO nanoparticle, particle diameter 50nm.
5g NiO nanoparticles are scattered in ultrasound 30 minutes in tetrahydrofuran solvent, after being uniformly dispersed, added 100g porous carbons continue ultrasound 20 minutes, high speed centrifugation, deionized water washing, obtain loading nickel oxide life after 40 DEG C of oven dryings Thing base N doping porous carbon, assemble battery as lithium ion battery negative material and test its charge-discharge performance.
Embodiment 3：
A kind of lithium battery load porous carbon negative pole material of nickel oxide bio-based N doping, it is characterised in that described biology Base N doping porous carbon is bamboo carbon, and the specific surface area of carbon material is 1500m2/ g, nitrogen element content 5.0wt.%.
Described load NiO nanoparticle, particle diameter 50nm.
5g NiO nanoparticles are scattered in ultrasound 30 minutes in tetrahydrofuran solvent, after being uniformly dispersed, added 100g porous carbons continue ultrasound 20 minutes, high speed centrifugation, deionized water washing, obtain loading nickel oxide life after 40 DEG C of oven dryings Thing base N doping porous carbon, assemble battery as lithium ion battery negative material and test its charge-discharge performance.
Embodiment 4：
A kind of lithium battery load porous carbon negative pole material of nickel oxide bio-based N doping, it is characterised in that described biology Base N doping porous carbon is bamboo carbon, and the specific surface area of carbon material is 2000m2/ g, nitrogen element content 8.0wt.%.
Described load NiO nanoparticle, particle diameter 50nm.
5g NiO nanoparticles are scattered in ultrasound 30 minutes in tetrahydrofuran solvent, after being uniformly dispersed, added 100g porous carbons continue ultrasound 20 minutes, high speed centrifugation, deionized water washing, obtain loading nickel oxide life after 40 DEG C of oven dryings Thing base N doping porous carbon, assemble battery as lithium ion battery negative material and test its charge-discharge performance.
In 100mAg-1Under current density, test respectively its first, 50 charge and discharge cycles specific capacities, concrete numerical value sees below Shown in table 1：
Table 1 loads the porous carbon negative pole material charge and discharge cycles specific capacity of nickel oxide bio-based N doping
The load nickel oxide bio-based N doping porous carbon of the preparation it can be seen from the data of table 1 is born as lithium ion battery Pole material first charge-discharge circulation specific capacity is up to 1084mAhg-1, far above the carbon material negative pole material commercially used 370mAhg-1, and still there is 510mAhg after undergoing 50 charge and discharge cycles-1Specific capacity value, equally far above commercial carbon material Negative material.Therefore, it can have extensive commercial value and answer as the alternative materials of commercial li-ion cell negative electrode material Use prospect.

Claims (3)

  1. A kind of 1. lithium battery load porous carbon negative pole material of nickel oxide bio-based N doping, it is characterised in that described bio-based N doping porous carbon is bamboo carbon, the one or two of bamboo shoots carbon, and the specific surface area of carbon material is 100~3000m2/ g, nitrogen Content is 0.1~10.0wt.%.
  2. 2. a kind of lithium battery according to claim 1 load porous carbon negative pole material of nickel oxide bio-based N doping, its Described load NiO nanoparticle is characterised by, particle diameter is 5~500nm.
  3. 3. a kind of lithium battery according to claim 1 load porous carbon negative pole material of nickel oxide bio-based N doping, its It is characterised by that preparation technology is：NiO nanoparticle is scattered in ultrasound 30 minutes in tetrahydrofuran solvent, waits to be uniformly dispersed Afterwards, add porous carbon and continue ultrasound 20 minutes, high speed centrifugation, deionized water is washed, and obtains loading nickel oxide life after oven drying Thing base N doping porous carbon.
CN201710893504.4A 2017-09-28 2017-09-28 A kind of lithium battery load porous carbon negative pole material of nickel oxide bio-based N doping Pending CN107706384A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110828801A (en) * 2019-11-05 2020-02-21 李彩琴 Lithium ion battery cathode material with phosphorus doped with lithium vanadate and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101780952A (en) * 2010-03-26 2010-07-21 上海交通大学 Method for preparing loading functional oxide porous carbon
CN104393284A (en) * 2014-11-17 2015-03-04 天津大学 Nickel oxide nano-particle loaded porous hard carbon sphere negative electrode material and preparation method thereof
CN106006636A (en) * 2016-05-19 2016-10-12 中国科学院青岛生物能源与过程研究所 Biomass-based nitrogen-doped porous carbon material, and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101780952A (en) * 2010-03-26 2010-07-21 上海交通大学 Method for preparing loading functional oxide porous carbon
CN104393284A (en) * 2014-11-17 2015-03-04 天津大学 Nickel oxide nano-particle loaded porous hard carbon sphere negative electrode material and preparation method thereof
CN106006636A (en) * 2016-05-19 2016-10-12 中国科学院青岛生物能源与过程研究所 Biomass-based nitrogen-doped porous carbon material, and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110828801A (en) * 2019-11-05 2020-02-21 李彩琴 Lithium ion battery cathode material with phosphorus doped with lithium vanadate and preparation method thereof
CN110828801B (en) * 2019-11-05 2021-08-03 萧县鑫辉源电池有限公司 Lithium ion battery cathode material with phosphorus doped with lithium vanadate and preparation method thereof

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