CN100376057C - Non-aqueous electrolyte lithium ion secondary cell - Google Patents

Non-aqueous electrolyte lithium ion secondary cell Download PDF

Info

Publication number
CN100376057C
CN100376057C CNB2004100627194A CN200410062719A CN100376057C CN 100376057 C CN100376057 C CN 100376057C CN B2004100627194 A CNB2004100627194 A CN B2004100627194A CN 200410062719 A CN200410062719 A CN 200410062719A CN 100376057 C CN100376057 C CN 100376057C
Authority
CN
China
Prior art keywords
sample
lithium ion
alloy powder
aqueous electrolyte
ion secondary
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.)
Expired - Fee Related
Application number
CNB2004100627194A
Other languages
Chinese (zh)
Other versions
CN1719656A (en
Inventor
王传福
渠冰
江文锋
董俊卿
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.)
BYD Co Ltd
Original Assignee
BYD Co Ltd
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 BYD Co Ltd filed Critical BYD Co Ltd
Priority to CNB2004100627194A priority Critical patent/CN100376057C/en
Publication of CN1719656A publication Critical patent/CN1719656A/en
Application granted granted Critical
Publication of CN100376057C publication Critical patent/CN100376057C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

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

Abstract

The present invention relates to a non-aqueous electrolyte lithium ion secondary battery which comprises a positive pole, a negative pole and non-aqueous electrolyte. The present invention is characterized in that the negative pole comprises a base plate and active substances of the negative pole attached on the base plate, wherein the active substances of the negative pole comprise base materials and the alloy powder of lithium and metal M, and the metal M is selected from at least one kind of groups composed of metal Be, Mg, Ti, Zr, V, Nb, Cr, Cu and Al. Because the active substances of the negative pole of the non-aqueous electrolyte lithium ion secondary battery supplied by the present invention contain the alloy powder of the lithium and the metal M, the charge-discharge efficiency of the battery for the first time and the overcharge-proof performance of the battery can be improved, the irreversible capacity of the negative pole is made up, the formation of lithium dendrites is reduced, the manufacture technology of the battery is simplified at the same time, and production cost is decreased.

Description

A kind of non-aqueous electrolyte lithium ion secondary cell
Technical field
The present invention relates to a kind of non-aqueous electrolyte lithium ion secondary cell.
Background technology
In recent years, the technology of lithium rechargeable battery is comparative maturity, compares with nickel-hydrogen secondary cell with using widely nickel-cadmium cell, and it is few that lithium rechargeable battery has a self discharge, the discharge voltage height, and energy density is high and recycle advantages such as the life-span is long.For improving the performance of lithium rechargeable battery, as the initial charge/discharge efficient and the cycle performance of battery, improve the utilization rate of positive active material, except that the performance and nonaqueous electrolytic solution of positive pole, it is quite important that negative pole seems.
The negative pole of lithium rechargeable battery generally by can mix and the material of impurity elimination lithium ion for example material with carbon element form.Material with carbon element can form a skim, i.e. SEI film on the material with carbon element top layer in first time charging process.This tunic generally is made up of the organic principle in lithium ion and the electrolyte, and having caused negative pole to take off the lithium ion that enter negative pole from positive pole in the first time in the discharge process can't all get back on the positive pole, thereby causes the first charge-discharge capacity of battery to descend.
In addition, when having too much Li to generate on the carbon material used as anode, these excessive Li will separate out at carbon material surface, form Li dendrite.In a single day these Li dendrites puncture diaphragm paper, will cause short circuit, cause potential safety hazard.So the lithium rechargeable battery that adopts material with carbon element to make negative pole must prevent to overcharge.
At JP2002313324, mention in the US20040002005 patent, adopt the powdered-metal that in the negative pole material, adds Li, the loss of capacity in the time of can remedying the negative pole first charge-discharge, thereby the capacity of raising battery.But if when having too much Li to exist on the carbon material used as anode, in case battery overcharges, excessive lithium will precipitate at negative pole.Wherein, the excessive lithium that is deposited on the lithium metal particle of negative pole is more prone to form crystal, i.e. the Li dendrite phenomenon.In a single day these Li dendrites puncture diaphragm paper, will cause short circuit, cause potential safety hazard.In addition, because the pure lithium metal that adopts is very active, in air, just be easy to react; so must adopt inert gas in the negative pole preparation process protects; prevent the aerial oxidation of lithium metal, very high to manufacturing technique requirent, production cost can improve greatly.
Summary of the invention
The objective of the invention is at existing above-mentioned defective in the prior art, a kind of non-aqueous electrolyte lithium ion secondary cell of negative electrode active material of the alloy powder that contains lithium-metal M is provided, thereby improve the first charge-discharge efficiency of battery and the overcharging resisting performance of battery, remedy the irreversible capacity of negative pole, effectively suppress the formation of Li dendrite, simplify cell production process and reduce its production cost.
For achieving the above object, the invention provides a kind of non-aqueous electrolyte lithium ion secondary cell, comprise positive pole, negative pole and nonaqueous electrolytic solution is characterized in that: described negative pole comprises substrate and the negative electrode active material that is attached on this substrate; Described negative electrode active material comprises base-material and contains the alloy powder of lithium-metal M, and described metal M is selected from by Be, Mg, Ti, Zr, V, Nb, Cr, at least a in the group that Cu and Al metal are formed.
In described negative electrode active material, the content of the alloy powder of described lithium-metal M is the 0.5%-20 weight % of described negative electrode active material total weight.
In the alloy powder of lithium-metal M that described negative electrode active material contains, the percentage that metal M accounts for described alloy powder total weight is 50%-90 weight %.
The alloy powder of the lithium-metal M that contains in the described negative electrode active material, its particle diameter are preferably smaller or equal to 100 μ m.
In the present invention, the base-material of described negative electrode active material has no particular limits, and can adopt base-material commonly used in the prior art, for example material with carbon element.Described material with carbon element can be non-graphitized charcoal, graphite or the charcoal that obtained by high-temperature oxydation by polyyne family macromolecule material, also can use other material with carbon element for example pyrolytic carbon, coke, organic polymer sinter, active carbon etc.; Described organic polymer sinter can be by with products therefrom after sintering and charing under the suitable temperature such as phenolic resins, epoxy resin.
In the present invention, the preparation of negative pole can be by negative electrode substrate is obtained with the powder compaction that contains described negative electrode active material.Described negative electrode substrate can adopt, for example, and Copper Foil or stainless steel substrates.It is even to add bonding agent and suitable solvent in the base-material of described negative electrode active material, and dried powder is made in oven dry at a certain temperature, this powder is evenly mixed with the alloy powder of a certain proportion of lithium-metal M under dry air, the gained powder is compressed under certain pressure forms negative pole on the substrate.Described bonding agent and solvent have no particular limits, and normally are used for the known bonding agent and the solvent of the negative pole preparation of lithium ion battery.
Described can mix and the positive pole of impurity elimination lithium has no particular limits can adopt the positive electrode of lithium rechargeable battery that is used for well known in the art as positive pole of the present invention.
In general, described positive pole comprises substrate and the positive active material that is attached on the substrate.Substrate can adopt aluminium foil or nickel screen.Described positive active material can be selected from metal sulfide or oxide, for example, can be to be selected from TiS 2, MoS 2, V 2O 5At least a with among the lithium composite xoide.These materials may be used alone, can also be used in combination.Wherein said lithium composite xoide contains the LiM that serves as principal component xO 2, wherein M is selected from least a among Co, Ni, Mn, Fe, Al, V and the Ti, and x changes according to battery charge or discharge condition, and its scope is between 0.05 to 1.10.
Described positive active material preferably uses the interlayer composite oxides that contain Li, and these lithium composite xoides can produce high voltage, and serves as the positive active material with good energy density.
In the present invention, anodal preparation method has no particular limits, and can be by positive electrode substrate is obtained with the powder compaction that contains described positive active material.The described powder that contains positive active material can contain bonding agent and solvent, and can contain conductive agent.
Described nonaqueous electrolytic solution has no particular limits, and can adopt the nonaqueous electrolytic solution that is used for lithium rechargeable battery well known in the art, for example, contains LiPF 6, LiBF 4, LiAsF 6, LiClO 4, LiCH 3SO 3, LiN (SO 2CF 3) 2, LiC (SO 2CF 3) 3, LiAlCl 4, LiSiF 6, LiB (C 6H 5) 4, LiCl or the electrolytical nonaqueous electrolytic solution of LiBr.These materials may be used alone, can also be used in combination.
The invention has the advantages that the initial charge/discharge efficient that improved lithium ion secondary battery negative pole and the ability of overcharging resisting, remedied the irreversible capacity of negative pole, employing adds the alloy powder of a certain amount of lithium-metal M in negative electrode active material, can make negative pole in air, place more than 3 hours at least, the negative electrode active material powder is still very stable, thereby can simplify the technology of battery production greatly and reduce production cost, and reduced the formation of Li dendrite.
Embodiment
Below the present invention is made further instruction.
Contain a certain amount of Li in lithium-metal M alloy powder, these powder are blended in the carbon negative electrode active material equably.When battery charge, react earlier between carbon negative electrode active material and the Li-M alloy powder.Li in the Li-M alloy powder deviates from earlier, is doped in the negative electrode active material and goes, and participates in the chemical reaction of negative pole.
The sedimentation potential of lithium ion on metal generally is lower than 0 volt (to lithium metal), and deposition potential is higher than 0 volt.That is to say that in a single day the lithium ion in the Li-M alloy powder is deviate from, a lot of so long as not overcharging, will be difficult to be deposited on the metal again.Because the specific capacity of Li is 4000mAh/g, even in alloy, the lithium ion that is discharged by Li is also far above graphite, and the theoretical specific capacity of native graphite has only 372mAh/g.Therefore, this part lithium ion can remedy the lithium ion of anodal material effectively because the loss that produces with negative electrode active material generation irreversible reaction, thereby has improved the utilization rate of anodal material, and battery capacity has also improved.
The scope that the Li-M alloy powder that the present invention adopts accounts for the negative electrode active material percentage by weight is between 0.5%-20%, and this is because when alloy powder amount very little the time, the lithium ion of release is few, to the efficiency for charge-discharge influence of entire cell not quite.And the ratio that accounts for when alloy powder must cause the minimizing of material with carbon element when higher, and this will influence the battery actual capacity.
In the Li-M alloy powder that the present invention adopts, the scope of the shared percentage by weight of metal M of non-lithium is 50%-90%.Too many when the metal proportion of non-lithium, the lithium ion of release has increased the materials of negative pole very little on the contrary.When the metal proportion of non-lithium very little, the making of lithium alloy is difficulty quite, and lithium content is too high, will cause the negative pole material to make in air, to the environment requirements harshness, has increased the cost that battery is made.And the scope of non-lithium metal of the present invention can be so that this alloy uses in dry air, thereby has reduced the cost and the manufacture craft of raw material and equipment.
The existence of the non-lithium metal M in the Li-M alloy powder of the present invention mainly has following two effects:
1. store a part of lithium at negative pole, when the battery initial charge, discharge,, improve anodal utilization rate with the lithium ion of the irreversible loss that remedies battery;
2. the holder of lithium ion when serving as over-charging of battery.When over-charging of battery, excessive lithium ion will be doped to negative pole and get on, if during the pure carbon material, these excessive lithium ions will precipitate on negative pole material surface, and generation dendrite causes potential safety hazard.When adding a certain amount of non-lithium metal, the sedimentation potential of lithium on these metals generally all is lower than the sedimentation potential of lithium ion on lithium metal.Therefore, the existence of non-lithium metal can store lithium ion excessive on the negative pole, and the discharge process subsequently discharges, and the Li dendrite phenomenon can not take place.
The alloy powder of lithium-metal M that negative electrode active material comprises, preferable particle size is smaller or equal to 100 μ m.This be since the particle diameter of material with carbon element generally at tens μ m, can be unfavorable for alloy powder stablizing in material with carbon element when the alloy powder particle diameter is too big, in case through repeatedly circulation, lithium ion constantly mixes and impurity elimination, the particle that the alloy powder particle diameter is too big will cause and comes off, cause material, influence the performance of battery.
[comparative example 1]
The preparation of negative pole: get 100 parts in negative electrode active material 059 type graphite, add (60%) 5 part of bonding agent polytetrafluoroethylene (PTFE) emulsion, add a certain amount of deionized water, mix.Drying at 120 ℃, then under the pressure of 5Mpa, is to be pressed into pie on the stainless steel substrates of 15mm at diameter, makes the negative plate that button cell is used.
Anodal preparation: get positive active material LiCoO 2100 parts, add 5 parts in bonding agent Kynoar (PVDF) powder, add 15 parts of conductive agent acetylene blacks again, in solvent N-methyl pyrrolidone (NMP), mix.Carrying out vacuum drying at 160 ℃, then under the pressure of 4Mpa, is to be pressed into pie on the nickel screen of 15mm at diameter, makes the positive plate that button cell is used.
The preparation of electrolyte: in ethylene carbonate (EC): the ratio of diethyl carbonate (DEC)=1: 1 is made solvent, adds a certain amount of LiPF 6Forming concentration is the electrolyte of 1mol/1.
With above-mentioned negative plate and positive plate and diaphragm paper, add electrolyte, make the button cell of CR2016 type.
[embodiment 1]
The preparation of negative pole: get 100 parts in negative electrode active material 059 type graphite, add (60%) 5 part of bonding agent polytetrafluoroethylene (PTFE) emulsion, add a certain amount of deionized water, mix.Dry at 120 ℃.In dry air, add 1 part of Li-Al alloy powder in the powder after oven dry, two kinds of powder mechanical mixture are even.The average grain diameter of this Li-Al alloy powder is 30 μ m, and the weight of Al accounts for 50% of Li-Al alloy powder weight.On diameter is the stainless steel substrates of 15mm, being pressed into pie under the pressure of 5Mpa, make the negative plate that button cell is used then.
The preparation of positive pole, electrolyte and the preparation of the integral body of battery are with comparative example 1.Obtain sample 1#.
Except what add in the negative plate of sample 1# is 3 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 2#.
Except what add in the negative plate of sample 1# is 5 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 3#.
Except what add in the negative plate of sample 1# is 7 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 4#.
Except what add in the negative plate of sample 1# is 9 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 5#.
Except what add in the negative plate of sample 1# is 11 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 6#.
Except what add in the negative plate of sample 1# is 13 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 7#.
Except what add in the negative plate of sample 1# is 15 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 8#.
Except what add in the negative plate of sample 1# is 17 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 9#.
Except what add in the negative plate of sample 1# is 19 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 10#.
Except what add in the negative plate of sample 1# is 21 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 11#.
[performance test]
For the button cell among comparative example and the embodiment, charging modes is a constant voltage charge, and the restriction electric current is 0.5mA/cm 2, cut-off current is 0.05mA/cm 2, final voltage is 4.2V; Discharge mode is a constant-current discharge, and discharging current is 0.5mA/cm 2, the cut-ff voltage of discharge is 3V.
Each sample test result sees Table 1.Experimental result shows, the weight that adds Al in negative active core-shell material accounts for 50% Li-Al alloy powder can improve the battery first charge-discharge efficiency.The weight ratio of negative active core-shell material and alloy powder is that 100: 5 (wt%) is proper.The capacity of carbon material used as anode reduced on the contrary when alloy powder content was too high, and the 2nd circulation volume has descended on the contrary.
[embodiment 2]
The preparation of negative pole: get 100 parts in negative electrode active material 059 type graphite, add (60%) 5 part of bonding agent polytetrafluoroethylene (PTFE) emulsion, add a certain amount of deionized water, mix.Dry at 120 ℃.In dry air, add 1 part of Li-Al alloy powder in the powder after oven dry, two kinds of powder mechanical mixture are even.The average grain diameter of this Li-Al alloy powder is 30 μ m, and the weight of Al accounts for 79% of Li-Al alloy powder weight.On diameter is the stainless steel substrates of 15mm, being pressed into pie under the pressure of 5Mpa, make the negative plate that button cell is used then.
The preparation of positive pole, electrolyte and the preparation of the integral body of battery are with comparative example 1.Obtain sample 1#.
Except what add in the negative plate of sample 1# is 3 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 2#.
Except what add in the negative plate of sample 1# is 5 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 3#.
Except what add in the negative plate of sample 1# is 7 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 4#.
Except what add in the negative plate of sample 1# is 9 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 5#.
Except what add in the negative plate of sample 1# is 11 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 6#.
Except what add in the negative plate of sample 1# is 13 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 7#.
Except what add in the negative plate of sample 1# is 15 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 8#.
Except what add in the negative plate of sample 1# is 17 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 9#.
Except what add in the negative plate of sample 1# is 19 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 10#.
Except what add in the negative plate of sample 1# is 21 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 11#.
Each sample test result sees Table 2.Experimental result shows, the weight that adds Al in negative active core-shell material accounts for 79% Li-Al alloy powder can improve the battery first charge-discharge efficiency.The weight ratio of negative active core-shell material and alloy powder is that 100: 9 (wt%) is proper.
[embodiment 3]
The preparation of negative pole: get 100 parts in negative electrode active material 059 type graphite, add (60%) 5 part of bonding agent polytetrafluoroethylene (PTFE) emulsion, add a certain amount of deionized water, mix.Dry at 120 ℃.Add 1 part of Li-Al alloy powder in the powder after oven dry, two kinds of powder mechanical mixture are even.The average grain diameter of this Li-Al alloy powder is 30 μ m, and the weight of Al accounts for 90% of Li-Al alloy powder weight.On diameter is the stainless steel substrates of 15mm, being pressed into pie under the pressure of 5Mpa, make the negative plate that button cell is used then.
The preparation of positive pole, electrolyte and the preparation of the integral body of battery are with comparative example 1.Obtain sample 1#.
Except what add in the negative plate of sample 1# is 3 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 2#.
Except what add in the negative plate of sample 1# is 5 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 3#.
Except what add in the negative plate of sample 1# is 7 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 4#.
Except what add in the negative plate of sample 1# is 9 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 5#.
Except what add in the negative plate of sample 1# is 11 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 6#.
Except what add in the negative plate of sample 1# is 13 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 7#.
Except what add in the negative plate of sample 1# is 15 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 8#.
Except what add in the negative plate of sample 1# is 17 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 9#.
Except what add in the negative plate of sample 1# is 19 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 10#.
Except what add in the negative plate of sample 1# is 21 parts of Li-Al alloy powders, and all the other are with sample 1#.Obtain sample 11#.
Each sample test result sees Table 3.Experimental result shows, the weight that adds Al in negative active core-shell material accounts for 79% Li-Al alloy powder can improve the battery first charge-discharge efficiency.The weight ratio of negative active core-shell material and alloy powder is that 100: 17 (wt%) is proper.
[embodiment 4]
The preparation of negative pole: get 100 parts in negative electrode active material 059 type graphite, add (60%) 5 part of bonding agent polytetrafluoroethylene (PTFE) emulsion, add a certain amount of deionized water, mix.Dry at 120 ℃.In dry air, add 8 parts of Li-Al alloy powders in the powder after oven dry, two kinds of powder mechanical mixture are even.The average grain diameter of this Li-Al alloy powder is 50 μ m, and the weight of Al accounts for 50% of Li-Al alloy powder weight.On diameter is the stainless steel substrates of 15mm, being pressed into pie under the pressure of 5Mpa, make the negative plate that button cell is used then.
The preparation of positive pole, electrolyte and the preparation of the integral body of battery are with comparative example 1.Obtain sample 1#.
Except the average grain diameter of the Li-Al alloy powder that adds in the negative plate of sample 1# is 41 μ m, and the weight of Al account for Li-Al alloy powder weight 60% beyond, all the other are with sample 1#.Obtain sample 2#.
Except the average grain diameter of the Li-Al alloy powder that adds in the negative plate of sample 1# is 34 μ m, and the weight of Al account for Li-Al alloy powder weight 70% beyond, all the other are with sample 1#.Obtain sample 3#.
Except the average grain diameter of the Li-Al alloy powder that adds in the negative plate of sample 1# is 30 μ m, and the weight of Al account for Li-Al alloy powder weight 80% beyond, all the other are with sample 1#.Obtain sample 4#.
Except the average grain diameter of the Li-Al alloy powder that adds in the negative plate of sample 1# is 27 μ m, and the weight of Al account for Li-Al alloy powder weight 90% beyond, all the other are with sample 1#.Obtain sample 5#.
Test result sees Table 4.
From the experimental result of table 4 as can be seen, the optimum content of non-lithium metal is 70% to 80% in the alloy powder.From table 4 also as can be seen the alloy powder content of non-lithium metal little to the battery influence, but non-lithium tenor is very little the time, and this alloy powder is made battery in air oxidized easily, causes losing activity, in air, do not make battery, will improve the cost of manufacture of battery; When non-lithium tenor was too high, lithium content was too low, and the alloy powder effect is little.Therefore, the content of non-lithium metal should be between 50%-90%.
[embodiment 5]
The preparation of negative pole: get 100 parts in negative electrode active material 059 type graphite, add (60%) 5 part of bonding agent polytetrafluoroethylene (PTFE) emulsion, add a certain amount of deionized water, mix.Dry at 120 ℃.In dry air, add 8 parts of Li-Be alloy powders in the powder after oven dry, two kinds of powder mechanical mixture are even.The average grain diameter of this Li-Be alloy powder is 44 μ m, and the weight of Be accounts for 70% of Li-Be alloy powder weight.On diameter is the stainless steel substrates of 15mm, being pressed into pie under the pressure of 5Mpa, make the negative plate that button cell is used then.
The preparation of positive pole, electrolyte and the preparation of the integral body of battery are with comparative example 1.Obtain sample 1#.
Except the average grain diameter that adds 8 parts Li-Mg alloy powder in the negative plate of sample 1# is 20 μ m, the weight of Mg account for Li-Mg alloy powder weight 70% beyond, all the other are with sample 1#.Obtain sample 2#.
Except the average grain diameter that adds 8 parts Li-Ti alloy powder in the negative plate of sample 1# is 18 μ m, the weight of Ti account for Li-Ti alloy powder weight 70% beyond, all the other are with sample 1#.Obtain sample 3#.
Except the average grain diameter that adds 8 parts Li-Zr alloy powder in the negative plate of sample 1# is 14 μ m, the weight of Zr account for Li-Zr alloy powder weight 70% beyond, all the other are with sample 1#.Obtain sample 4#.
Except the average grain diameter that adds 8 parts Li-V alloy powder in the negative plate of sample 1# is 15 μ m, the weight of V account for Li-V alloy powder weight 70% beyond, all the other are with sample 1#.Obtain sample 5#.
Except the average grain diameter that adds 8 parts Li-Nb alloy powder in the negative plate of sample 1# is 13 μ m, the weight of Nb account for Li-Nb alloy powder weight 70% beyond, all the other are with sample 1#.Obtain sample 6#.
Except the average grain diameter that adds 8 parts Li-Cr alloy powder in the negative plate of sample 1# is 17 μ m, the weight of Cr account for Li-Cr alloy powder weight 70% beyond, all the other are with sample 1#.Obtain sample 7#.
Except the average grain diameter that adds 8 parts Li-Cu alloy powder in the negative plate of sample 1# is 19 μ m, the weight of Cu account for Li-Cu alloy powder weight 70% beyond, all the other are with sample 1#.Obtain sample 8#.
Except the average grain diameter that adds 8 parts Li-Al alloy powder in the negative plate of sample 1# is 30 μ m, the weight of Al account for Li-Al alloy powder weight 70% beyond, all the other are with sample 1#.Obtain sample 9#.
Test result sees Table 5.
From experimental result as can be seen, Be, Mg, Ti, Zr, V, Nb, Cr, Cu is the same with Al, when forming alloy with Li, can improve battery first charge-discharge efficiency and capacity effectively.
[embodiment 6]
The preparation of negative pole: get 100 parts in negative electrode active material 059 type graphite, add (60%) 5 part of bonding agent polytetrafluoroethylene (PTFE) emulsion, add a certain amount of deionized water, mix.Dry at 120 ℃.In dry air, add 8 parts of Li-Al alloy powders in the powder after oven dry, two kinds of powder mechanical mixture are even.The average grain diameter of this Li-Al alloy powder is 30 μ m, and the weight of Al accounts for 70% of Li-Al alloy powder weight.On diameter is the stainless steel substrates of 15mm, being pressed into pie under the pressure of 5Mpa, make the negative plate that button cell is used then.
The preparation of anodal, electrolyte and the integral body system of battery each with comparative example 1.Obtain sample 1#.
Sample 1# is carried out the 1C charging overcharge experiment.
Find that by experimental result comparative example 1 is only being charged to 4.6V, and embodiment 6 can be charged to 4.8V.This explanation the present invention can effectively prevent over-charging of battery.
The comparison of table 1 embodiment 1 and comparative example 1
No. The Li-M alloy Negative pole material: alloy powder (wt%) First charge-discharge efficiency (%) Discharge capacity (mAh/g)
M M content (accounting for alloy powder wt%) The 1st circulation The 2nd circulation
Comparative example 1 - - 100∶0 88.1 305.2 295.6
Embodiment 1 1# Al 50 100∶1 92.3 325.3 324.1
2# Al 50 100∶3 98.6 345.6 344.2
3# Al 50 100∶5 101.2 361.1 342.3
4# Al 50 100∶7 108.9 372.3 338.7
5# Al 50 100∶9 118.3 385.6 332.1
6# Al 50 100:11 133.4 391.2 321.9
7# Al 50 100∶13 171.8 405.1 307.3
8# Al 50 100∶15 198.2 419.6 301.1
9# Al 50 100∶17 215.2 438.2 301.2
10# Al 50 100∶19 235.1 480.1 288.5
11# Al 50 100∶21 261.9 501.3 269.4
The comparison of table 2 embodiment 2 and comparative example 1
No. The Li-M alloy Negative pole material: alloy powder (wt%) First charge-discharge efficiency (%) Discharge capacity (mAh/g)
M M content (accounting for alloy powder wt%) The 1st circulation The 2nd circulation
Comparative example 1 - - 100∶0 88.1 305.2 295.6
Embodiment 2 1# Al 79 100∶1 89 311.1 307.7
2# Al 79 100∶3 90.2 318.4 316.4
3# Al 79 100∶5 92.1 327.6 324.5
4# Al 79 100∶7 95.5 337.3 331.4
5# Al 79 100∶9 98.8 342.6 335.1
6# Al 79 100∶11 105.4 361.2 331.2
7# Al 79 100∶13 114.2 375.8 321.7
8# Al 79 100∶15 130.7 389.4 315.6
9# Al 79 100∶17 167.8 401.9 309.2
10# Al 79 100∶19 201.2 421.7 301.1
11# Al 79 100∶21 230.4 450.3 298.4
The comparison of table 3 embodiment 3 and comparative example 1
No. The Li-M alloy Negative pole material: alloy powder (wt%) First charge-discharge efficiency (%) Discharge capacity (mAh/g)
M M content (accounting for alloy powder wt%) The 1st circulation The 2nd circulation
Comparative example 1 - - 100∶0 88.1 305.2 295.6
Embodiment 3 1# Al 90 100∶1 88.9 307.4 304.1
2# Al 90 100∶3 89.6 312.3 306.5
3# Al 90 100∶5 91.5 318.6 315.1
4# Al 90 100∶7 92.8 324.3 319.2
5# Al 90 100∶9 94.4 329.6 321.9
6# Al 90 100∶11 96.1 333.2 325.4
7# Al 90 100∶13 97.5 337.8 330.5
8# Al 90 100∶15 98.3 339.4 334.6
9# Al 90 100∶17 99.6 345.2 338.1
10# Al 90 100∶19 101.2 351.7 324.1
11# Al 90 100∶21 106.3 361.2 315.4
The comparison of table 4 embodiment 4 and comparative example 1
No. The Li-M alloy Negative pole material: alloy powder (wt%) First charge-discharge efficiency (%) Discharge capacity (mAh/g)
M M content (accounting for alloy powder wt%) The 1st circulation The 2nd circulation
Comparative example 1 - - 100∶0 88.1 305.2 295.6
Embodiment 4 1# Al 50 100∶8 99.5 345.5 333.6
2# Al 60 100∶8 98.7 341.4 334.1
3# Al 70 100∶8 98.4 337.6 332.2
4# Al 80 100∶8 98.3 337.3 331.4
5# Al 90 100∶8 97.1 327.6 321.7
The comparison of table 5 embodiment 5 and comparative example 1
No. The Li-M alloy Negative pole material: alloy powder (wt%) First charge-discharge efficiency (%) Discharge capacity (mAh/g)
M M content (accounting for alloy powder wt%) The 1st circulation The 2nd circulation
Comparative example 1 - - 100∶0 88.1 305.2 295.6
Embodiment 5 1# Be 70 100∶8 98.2 331.5 307.7
2# Mg 70 100∶8 97.5 319.7 316.7
3# Ti 70 100∶8 97.6 325.3 315.8
4# Zr 70 100∶8 96.8 311.3 302.1
5# V 70 100∶8 98.4 340.1 335.3
6# Nb 70 100∶8 98.1 331.7 321.6
7# Cr 70 100∶8 97.4 325.8 321.1
8# Cu 70 100∶8 95.1 303.4 301.6
9# Al 70 100∶8 98.4 337.6 332.2

Claims (11)

1. a non-aqueous electrolyte lithium ion secondary cell comprises positive pole, and negative pole and nonaqueous electrolytic solution is characterized in that: described negative pole comprises substrate and the negative electrode active material that is attached on this substrate; Described negative electrode active material comprises base-material and contains the alloy powder of lithium-metal M, and described metal M is selected from by Be, Mg, Ti, Zr, V, Nb, Cr, at least a in the group that Cu and Al metal are formed; The content of the alloy powder of described lithium-metal M is the 0.5%-20 weight % of described negative electrode active material total weight.
2. non-aqueous electrolyte lithium ion secondary cell according to claim 1, in the alloy powder of lithium-metal M that wherein said negative electrode active material contains, the percentage that metal M accounts for described alloy powder total weight is 50%-90 weight %.
3. non-aqueous electrolyte lithium ion secondary cell according to claim 1 and 2, the particle diameter of the alloy powder of wherein said lithium-metal M are smaller or equal to 100 μ m.
4. non-aqueous electrolyte lithium ion secondary cell according to claim 1, wherein said base-material are material with carbon element.
5. non-aqueous electrolyte lithium ion secondary cell according to claim 4, wherein said material with carbon element are non-graphitized charcoal, graphite, pyrolytic carbon, coke, organic polymer sinter and/or active carbon.
6. non-aqueous electrolyte lithium ion secondary cell according to claim 5, wherein said organic polymer sinter are by with products therefrom after sintering and the charing at high temperature of polyyne, phenolic resins or epoxy resin.
7. non-aqueous electrolyte lithium ion secondary cell according to claim 1, wherein said positive pole comprise substrate and the positive active material that is attached on this substrate.
8. non-aqueous electrolyte lithium ion secondary cell according to claim 7, wherein said positive active material are metal sulfide and/or oxide.
9. non-aqueous electrolyte lithium ion secondary cell according to claim 8, wherein said positive active material is for being selected from by TiS 2, MoS 2, V 2O 5At least a in the group of forming with lithium composite xoide.
10. non-aqueous electrolyte lithium ion secondary cell according to claim 9, wherein said lithium composite xoide are LiM xO 2, wherein M is selected from least a among Co, Ni, Mn, Fe, Al, V and the Ti, and x changes according to battery charge or discharge condition, and its scope is between 0.05 to 1.10.
11. non-aqueous electrolyte lithium ion secondary cell according to claim 1, wherein said nonaqueous electrolytic solution is to contain LiPF 6, LiBF 4, LiAsF 6, LiClO 4, LiCH 3SO 3, LiN (SO 2CF 3) 2, LiC (SO 2CF 3) 3, LiAlCl 4, LiSiF 6, LiB (C 6H 5) 4, LiCl and/or the electrolytical nonaqueous electrolytic solution of LiBr.
CNB2004100627194A 2004-07-07 2004-07-07 Non-aqueous electrolyte lithium ion secondary cell Expired - Fee Related CN100376057C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2004100627194A CN100376057C (en) 2004-07-07 2004-07-07 Non-aqueous electrolyte lithium ion secondary cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2004100627194A CN100376057C (en) 2004-07-07 2004-07-07 Non-aqueous electrolyte lithium ion secondary cell

Publications (2)

Publication Number Publication Date
CN1719656A CN1719656A (en) 2006-01-11
CN100376057C true CN100376057C (en) 2008-03-19

Family

ID=35931433

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2004100627194A Expired - Fee Related CN100376057C (en) 2004-07-07 2004-07-07 Non-aqueous electrolyte lithium ion secondary cell

Country Status (1)

Country Link
CN (1) CN100376057C (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102487151B (en) * 2010-12-02 2014-10-08 比亚迪股份有限公司 Lithium ion secondary battery
CN115224253A (en) 2016-02-23 2022-10-21 特斯拉公司 Elemental metal and carbon mixtures for energy storage devices
CN117154031A (en) * 2017-02-21 2023-12-01 特斯拉公司 Pre-lithiated energy storage device
CN109244473B (en) * 2018-10-08 2022-03-08 电子科技大学 Lithium alloy strip and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1338129A (en) * 1999-11-29 2002-02-27 松下电器产业株式会社 Non-aqueous electrolyte cell
CN1501542A (en) * 2002-07-15 2004-06-02 三星Sdi株式会社 Lithium secondary battery and a method for preparing the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1338129A (en) * 1999-11-29 2002-02-27 松下电器产业株式会社 Non-aqueous electrolyte cell
CN1501542A (en) * 2002-07-15 2004-06-02 三星Sdi株式会社 Lithium secondary battery and a method for preparing the same

Also Published As

Publication number Publication date
CN1719656A (en) 2006-01-11

Similar Documents

Publication Publication Date Title
EP2071651B1 (en) Negative electrode and rechargeable lithium battery including same
KR101711985B1 (en) Negative active material for rechargeable lithium battery, rechargeable lithium battery including the same, and method of preparing negative electrode for rechargeable lithium battery including the same
KR100646546B1 (en) Negative active material for lithium secondary battery and method of preparing same
CN100367543C (en) Lithium alloy composite material and its preparing method, minus pole material, negative pole structure and lithium secondary cells
EP1936731A1 (en) Rechargeable lithium battery
CN105742713B (en) All-solid-state polymer lithium battery
KR101265195B1 (en) Positive electrode for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same
KR20160088181A (en) Negative active material for rechargeable lithium battery, method of preparing the same and rechargeable lithium battery including the same
EP2624340A1 (en) Negative active material, method of preparing the same, negative electrode for lithium secondary battery including negative active material, and lithium secondary battery including negative electrode
KR20030081160A (en) Battery
KR102631720B1 (en) Manufacturing method of lithium secondary battery
CN112490518B (en) Positive electrode lithium supplement additive, preparation method thereof, positive electrode and lithium ion battery
KR101775542B1 (en) Negative active material for rechargeable lithium battery, method of preparing the same, and negative electrode and rechargeable lithium battery including same
US10923717B2 (en) Lithium ion secondary battery
US9356283B2 (en) Positive active material for rechargeable lithium battery and rechargeable lithium battery
KR101375326B1 (en) Composite anode active material, method of preparing the same, anode and lithium battery containing the material
CN116706050B (en) Medium-low nickel monocrystal ternary positive electrode material, preparation method thereof and battery
US9077029B2 (en) Negative active material for rechargeable lithium battery and rechargeable lithium battery including the same
CN100376057C (en) Non-aqueous electrolyte lithium ion secondary cell
US9947925B2 (en) Negative electrode for lithium-ion secondary battery
US9385375B2 (en) Positive electrode for rechargeable lithium battery and rechargeable lithium battery including same
KR101397019B1 (en) Composite anode active material, method of preparing the same, and anode and lithium battery containing the material
US9496548B2 (en) Negative active material for rechargeable lithium battery, method for preparing same, and rechargeable lithium battery including same
KR20220048837A (en) Positive electrode for lithium secondary battery, and rechargebaly lithium battery including the same
EP3982460A1 (en) Manufacturing method of lithium secondary battery

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20080319

Termination date: 20190707

CF01 Termination of patent right due to non-payment of annual fee