CN103972507B - A kind of negative electrode active material, negative plate and pulse buffer cell, battery pack and power battery module containing this negative plate - Google Patents

A kind of negative electrode active material, negative plate and pulse buffer cell, battery pack and power battery module containing this negative plate Download PDF

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CN103972507B
CN103972507B CN201310035918.5A CN201310035918A CN103972507B CN 103972507 B CN103972507 B CN 103972507B CN 201310035918 A CN201310035918 A CN 201310035918A CN 103972507 B CN103972507 B CN 103972507B
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negative
active material
battery pack
electrode active
nanometer
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CN103972507A (en
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屈丽辉
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BYD Co Ltd
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BYD Co Ltd
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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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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

Abstract

The invention provides a kind of negative electrode active material, this active material comprises graphite and additive；Described additive is nano Co Fe2O4, nanometer Fe1.5Ti0.3O3, nanometer Li2FeSiO4With at least one in Si/C nanofiber composite.Present invention also offers a kind of negative plate, the pulse buffer cell containing this negative plate and a kind of pulse buffer battery pack and power battery module.The power battery module of the present invention has high capability retention, and pulse battery pack has good protective effect to power battery module.

Description

A kind of negative electrode active material, negative plate and the pulse buffer monomer containing this negative plate Battery, battery pack and power battery module
Technical field
The invention belongs to electrokinetic cell field, particularly relate to a kind of negative electrode active material, negative plate and contain this negative plate Pulse buffer battery, battery pack and power battery module.
Background technology
In recent years, along with impact and the high-level requirement of environmental protection of oil crisis, hybrid vehicle, pure power vehicle Become the Main Trends of The Development of automobile.And the topmost power resources as hybrid vehicle and pure electric automobile fill Put vehicle mounted dynamic battery module and become the focus of research.
The skidding mode of hybrid vehicle and pure electric automobile is different from conventional fuel oil car, the braking of fuel vehicle Mode is mechanical brake, and which brake wear is serious, and produces substantial amounts of heat and can cause heat fading phenomenon, and mixes dynamic The skidding mode of power automobile and pure electric automobile is regenerative braking mode, and the energy back produced when it is by brake is to car Carry battery, both avoided the waste of energy, continual mileage can be improved again.And in hybrid vehicle and pure electric automobile driving Journey is very important.But power battery module is charged by short time pulse current when energy back is to brake.Existing Vehicle mounted dynamic battery module be usually lithium ion power battery module, this module is by some lithium ion single battery strings joint groups Become.But battery module typically at more than 200A, duration 10S, the highest electric current, is produced strong by the pulse current of brake Big impact, the damage of battery is the most serious, often occurs that electrolyte side reaction aggravation or negative pole produce Li dendrite, can serious shadow Ring safety and the life-span of battery.
CN102263300 discloses a kind of vehicle mounted dynamic battery module.This vehicle mounted dynamic battery module includes electrokinetic cell Group, power battery pack has some power cells to be composed in series；Also include the pulse buffer battery in parallel with power battery pack Group, pulse buffer battery pack is composed in series by some pulse buffer cells；The both end voltage of power battery pack is delayed with pulse The both end voltage rushing battery pack is equal, and the both end voltage of power battery pack is 1 with the polarization resistance ratio of pulse buffer battery pack: 0.5-1:0.1.The vehicle mounted dynamic battery module of the present invention can effectively resist the injury that it is caused by brake pulse current；At arteries and veins After rushing rush of current, can effectively keep cycle performance and the security performance of vehicle mounted dynamic battery module.But this patent The technical scheme being previously mentioned, owing to being limited by material and process conditions, can only accomplish that the polarization resistance of pulse buffer battery pack is 0.5-0.1 times of power battery pack.This pulse buffer battery pack is limited to the protective capability of power battery pack.
Summary of the invention
The present invention solves electrokinetic cell when high power discharge and recharge, big current versus cell module produces powerful impact Technical problem, it is provided that a kind of can carry out high power, the negative electrode active material of high current charge-discharge, negative plate and containing this negative pole The pulse buffer battery of sheet, battery pack very power battery module.
The invention provides a kind of negative electrode active material, this active material comprises graphite and additive；Described additive is Nano Co Fe2O4, nanometer Fe1.5Ti0.3O3, nanometer Li2FeSiO4With at least one in Si/C nanofiber composite.
Present invention also offers a kind of negative plate, this negative plate includes negative current collector and is coated on negative pole currect collecting surface Negative material；Described negative material includes negative electrode active material, conductive agent and binding agent；Described negative electrode active material is this Bright described negative electrode active material.
Present invention also offers a kind of pulse buffer cell, described pulse buffer cell include cover plate, housing, Battery core and electrolyte, described battery core and electrolyte is sealed in battery container, and described cover plate is hermetically connected with the shell；Described battery core Including positive plate, negative plate and the barrier film being arranged between positive plate and negative plate；Wherein, described negative plate is institute of the present invention The negative plate stated.
Present invention also offers a kind of pulse buffer battery pack, described pulse buffer battery pack is pulse of the present invention Buffering cells in series forms.
Present invention also offers a kind of power battery module, described module includes power battery pack and the pulse buffer of parallel connection Battery pack；The both end voltage of described power battery pack is equal with the both end voltage of pulse buffer battery pack；Described pulse buffer electricity Pond group is pulse buffer battery pack of the present invention.
The pulse buffer battery pack that the present invention prepares takes into account little impedance and small size, the protection energy to power battery pack Power is greatly improved.
Detailed description of the invention
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with Embodiment, is further elaborated to the present invention.Should be appreciated that specific embodiment described herein is only in order to explain The present invention, is not intended to limit the present invention.
The invention provides a kind of negative electrode active material, this active material comprises graphite and additive；Described additive is Nano Co Fe2O4, nanometer Fe1.5Ti0.3O3, nanometer Li2FeSiO4With at least one in Si/C nanofiber composite.
In prior art, the particle of general negative active core-shell material graphite is the biggest, exists between its particle and particle Gap, contacts bad.Nano level CoFe2O4、Fe1.5Ti0.3O3、Li2FeSiO4It is little with the particle of Si/C nanofiber composite, Specific capacity is high, and electrical conductivity is big, and power-performance is good.Nano level CoFe is added in general active material2O4、Fe1.5Ti0.3O3、 Li2FeSiO4With Si/C nanofiber composite, the gap between active material graphite can well be filled, make active material Between path shorten and broaden, thus improve the electrical conductivity of negative plate.
Nano Co Fe of the present invention2O4Can manufacture voluntarily, it is also possible to buy.Such as nano Co Fe2O4Can use such as Prepared by lower preparation method: by Fe (NO3)3·9H2O Yu Co (NO3)2·6H2O(mol ratio 2:1) add in graphite, stirring at normal temperature 30min, adds NaOH regulation pH value and makes pH=10, stir 30min.Then 180 DEG C of heating 20h, cooled and filtered, rinse, and is dried After.
Nanometer Fe of the present invention1.5Ti0.3O3Can manufacture voluntarily, it is also possible to buy.Such as nanometer Fe1.5Ti0.3O3Permissible Following preparation method is used to prepare: Ti (OBu)4Add in alcohol, then add HNO3, obtain solution A.Fe(NO3)3·9H2O Join in distilled water, obtain solution B.Being added by B in A, stir 30min, spent glycol amine correction pH value makes pH=3, places 7 More than it.Then 200 DEG C of heating, obtain solid product, solid product is used distilled water cleaning, drying, fires 2h i.e. for 300 DEG C Can.
Nanometer Li of the present invention2FeSiO4Can manufacture voluntarily, it is also possible to buy.Such as nanometer Li2FeSiO4Can adopt Prepare with following preparation method: by Fe (NO3)3·9H2O adds in distilled water, is subsequently adding CH3COOLi 2H2O, adds again Entering citric acid and (C2H5O) 4Si, more than stirring at normal temperature 3h, then 80 degrees Celsius of evaporations, are allowed to gel, are produced by gel Thing high temperature 600 DEG C in an inert atmosphere calcining 10h, obtains end product.
Si/C nanofiber composite of the present invention is to have silicon in the surface attachment of carbon.Its preparation method is: high temperature Under the conditions of (more than 400 DEG C), silane gas is blended in inert gas, heats together with carbon, make siliceous deposits on the surface of carbon. Material with carbon element can use CNT, it is possible to use graphite, hard carbon or carbon black etc..
According to negative electrode active material provided by the present invention, it is preferable that graphite and additive in described negative electrode active material Mass ratio be 100:1-20.More preferably 100:8-12.Graphite is as negative active core-shell material, and its capacity is with service time of battery Decay smaller, but, particle is big, and electrical conductivity is little, and specific capacity is low.And the advantage of additive to be particle little, specific capacity is high, electricity Conductance is big, and power-performance is good, and shortcoming is that capacity is bigger with the attenuation ratio of service time of battery.And the stone in the range of aforementioned proportion Ink and additive can play its advantage and evade shortcoming, produces power-performance and the most reasonable battery of capacity.
According to negative electrode active material provided by the present invention, in order to reduce cost, it is preferable that the average grain diameter of described graphite For 1.5-12 micron.
According to negative electrode active material provided by the present invention, it is preferable that described nano Co Fe2O4, nanometer Fe1.5Ti0.3O3、 Nanometer Li2FeSiO4Average grain diameter be respectively 50-200 nanometer；A diameter of 50-200 of described Si/C nanofiber composite receives Rice.Length for Si/C nanofiber composite has no particular limits, if can fill with in graphite hole.This Particle diameter is far smaller than the particle diameter of graphite, can well fill the hole of graphite.
Present invention also offers a kind of negative plate, this negative plate includes negative current collector and is coated on negative pole currect collecting surface Negative material；Described negative material includes negative electrode active material, cathode conductive agent and negative electrode binder；Described negative electrode active material Matter is negative electrode active material of the present invention.
According to negative plate provided by the present invention, it is preferable that the dressing thickness of described negative plate is graphite average grain diameter 2-3 times.This relatively thin dressing thickness can shorten the distance that lithium ion moves, and accelerates the deintercalation of lithium ion, reduces big electric current Polarization during charge and discharge, is suitable for high-power discharge and recharge.
According to negative plate provided by the present invention, it is preferable that the compacted density of described negative plate is 0.6-1.3g/cm3.Should In the range of compacted density both can ensure that electrokinetic cell had certain energy density, can ensure that pole piece has loose many simultaneously The feature in hole, reduces the resistance of lithium ion infiltration, can be with high-power discharge and recharge.
In the present invention, can use and well known to a person skilled in the art various cathode conductive agent, it is preferable that described negative conductive Agent is at least one in CNT, Graphene, carbon black.
In the present invention, can use and well known to a person skilled in the art various negative electrode binder, it is preferable that described negative pole bonds Agent uses the mixture of cellulose-based polymer and rubber latex, such as the mixture of cellulose-based polymer Yu butadiene-styrene rubber.
In the present invention, can use and well known to a person skilled in the art various negative current collector, such as, described negative current collector For stamped metal, metal forming, net metal or foamed metal.
Present invention also offers a kind of pulse buffer cell, described pulse buffer cell include cover plate, housing, Battery core and electrolyte, described battery core and electrolyte is sealed in battery container, and described cover plate is hermetically connected with the shell；Described battery core Including positive plate, negative plate and the barrier film being arranged between positive plate and negative plate；Wherein, described negative plate is institute of the present invention The negative plate stated.
Described positive plate includes positive electrode active materials, plus plate current-collecting body, positive conductive agent and binding agent.
The active material of described positive pole can use and well known to a person skilled in the art various active material, and the present invention does not has spy Do not limit.Can be such as the LiFePO 4 of the feature with Large ratio surface, small particle, high conductivity, lithium manganese phosphate, mangaic acid One or more mixing of the common lithium ion anode active materials such as lithium, lithium cobalt oxide, lithium nickel oxygen, binary or ternary material.
Positive conductive agent, positive electrode binder and the plus plate current-collecting body of the present invention is various positive conductive commonly used in the art Agent, positive electrode binder and plus plate current-collecting body.Such as: positive conductive agent is carbon black；Positive electrode binder is Kynoar.Positive pole collection Fluid is aluminium foil；Positive plate dressing thickness, compacted density are depending on the technique of concrete material and negative pole.
Described barrier film is various barrier films commonly used in the art, and the present invention is not particularly limited.Can be polypropylene screen, poly-second Alkene film or the lithium ion battery such as propylene and ethylene copolymer film commonly use barrier film.
It is high that described electrolyte comprises lithium salts and solvent, preferably electrical conductivity, the electrolyte that temperature range is wide.Wherein, electrolyte Lithium salts can be selected from lithium hexafluoro phosphate (LiPF6), lithium perchlorate (LiClO4), LiBF4 (LiBF4), hexafluoroarsenate lithium (LiAsF6), hexafluorosilicic acid lithium (LiSiF6), tetraphenylboronic acid lithium (LiB (C6H5) 4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl4) and fluorohydrocarbon base Sulfonic Lithium (LiC (SO2CF3)3), LiCH3SO3、LiN(SO2CF3)2In one Plant or multiple.Electrolyte can be selected from chain acid esters and ring-type acid esters mixed solution, and wherein chain acid esters can be carbonic acid diformazan Ester (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC) and its One or more in its fluorine-containing, sulfur-bearing or the chain organosilane ester containing unsaturated bond.Ring-type acid esters can be ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton (γ-BL), sultone and other fluorine-containing, sulfur-bearing Or one or more in the ring-type organosilane ester containing unsaturated bond.In described electrolyte, the concentration of electrolyte lithium salt is permissible For 0.1-2mol/L.
Described battery case can use the housing that well known to a person skilled in the art various material, has no particular limits, as It can be the battery case materials that the lithium ion batteries such as box hat, aluminum hull, plastics, aluminum plastic film are conventional.The structure of pole piece and preparation method All can use structure and the preparation method of this area routine.
Present invention also offers a kind of pulse buffer battery pack, described pulse buffer battery pack is pulse of the present invention Buffering cells in series forms.
Present invention also offers a kind of power battery module, described module includes power battery pack and the pulse buffer of parallel connection Battery pack；The both end voltage of described power battery pack is equal with the both end voltage of pulse buffer battery pack；Described pulse buffer electricity Pond group is pulse buffer battery pack of the present invention.
The pulse buffer battery pack that the present invention provides, its polarization resistance is 0.5-0.05 times of power battery pack.
The present invention is described in further detail by application specific embodiment below.
Comparative example 1
Power battery pack CC1 is made up of 100 electrokinetic cell monomers, and the making parameter of each electrokinetic cell monomer is: just Pole active material is LiFePO4, dressing thickness is 60 μm, and dressing area is 1.26m2, dressing volume density is 2.2g/cm3, negative pole Active material is graphite, and dressing thickness is 50 μm, and dressing area is 1.32m2, dressing volume density is 1.1g/cm3, cell Capacity is 20Ah, and voltage is 3.2V, and internal resistance is 2m Ω, and inclusion internal resistance is 200m Ω.
Comparative example 2
Use the pulse buffer cell CA1 in patent CN102263300 embodiment 1, with CC1 after 133 CA1 series connection Parallel connection, forms the fast CC2 of electrokinetic cell mould.
Embodiment 1-80
1, power battery pack: CC1；
2, pulse buffer cell A1-A80: positive electrode active materials, dressing thickness, dressing area, dressing volume density, negative Pole active material, dressing thickness, dressing area, dressing volume density are shown in Table 1；
3, pulse buffer battery pack B1-B80: be in series by multiple pulse buffer cell A1-A80 respectively.Pulse The battery cell quantity of buffer battery group, the capacity of cell, voltage, internal resistance, the internal resistance of pulse buffer battery pack are shown in Table 2；
4, power battery module: by power battery pack CC1 formation power in parallel with pulse buffer battery pack B1-B80 respectively Battery module C1-C80.
Table 1
Remarks: 1, positive pole volume density: LiFePO4: 2.2g/cm3；LiCoO2: 3.8g/cm3；LiMn2O4: 2.8g/ cm3LiMnPO4: 1.9g/cm3；
2, in bracket being its average grain diameter after graphite and additive, Si/C's is diameter, unit be respectively micron and Nanometer.
Table 2
Method of testing and result
1, the electrokinetic cell in the pulse buffer cell in embodiment, pulse buffer battery pack and comparative example is carried out Following test, the results are shown in Table 3.
The internal resistance of cell is tested: under room temperature, by cell with I0.2CCharging 2h, then with I10CCharging 1s, measures simultaneously Voltage V at the end of 10C charging3Continuing charging with 0.2C after, surveying cell voltage after 10s again is V2, internal resistance computing formula is R= (V3-V2)/I10C-I0.2C。
Battery capacity is tested: under room temperature, by battery with 0.2C electric current constant-current charge to the charge cutoff voltage of various batteries, After with 0.2C electric current constant-current discharge to the discharge cut-off voltage of various batteries, obtain the initial capacity of battery.
The voltage range of various batteries is: LiFePO4: 2.0-3.6V；LiCoO2: 2.5-4.2V；LiMn2O4: 2.5- 4.4V；LiMnPO4: 3-4.8V；LiMn2O4/Li4/3Ti5/3O4: 1.8-3V.
Internal resistance ratio=pulse buffer internal resistance of single cell (A1-A80) * number of batteries/power battery pack internal resistance (CC1)
Capacity Ratio=pulse buffer cell capacity (A1-A80) * number of batteries/electrokinetic cell pool-size (CC1).
2, by the power battery module C1-C80 in embodiment and power battery pack CC1 in comparative example 1 and comparative example 2 The fast CC2 of electrokinetic cell mould test as follows, the results are shown in Table 3.
Initial capacity is tested: at normal temperatures, 100A charges to 360V, shelves 10min, 100A and is discharged to 200V.Record is put Capacitance is C0
Pulse cycle is tested: at normal temperatures, 600A(or 6000A) charging 10s, 60A(or 200A) electric discharge 100s, so follows Ring 300,000 times.
Recover volume test: at normal temperatures, 100A charges to 360V, shelves 10min, 100A and is discharged to 200V.Record is put Capacitance is C1.
After 300000 circulations, capability retention calculates: C1/C0.
Table 3
From table 3 it can be seen that the electrokinetic cell module having added buffer battery group of the present invention, after 600A circulates 300,000 times Capability retention is all higher than 69%, and the battery modules of comparative example 1 capability retention after circulating 1,000,000 times at 600A only has 40%, comparative example 2 is 46%；The electrokinetic cell module having added buffer battery group of the present invention, capacity after 6000A circulates 300,000 times Conservation rate is all higher than 10%, and the battery modules of comparative example 1 capability retention after circulating 1,000,000 times at 6000A is 0, comparative example 2 is 0.Illustrate that the pulse buffer battery pack of the present invention has good protective effect to electrokinetic cell module.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention Any amendment, equivalent and the improvement etc. made within god and principle, should be included within the scope of the present invention.

Claims (9)

1. a negative electrode active material, it is characterised in that: this active material comprises graphite and additive；Described additive is nanometer CoFe2O4, nanometer Fe1.5Ti0.5O3, nanometer Li2FeSiO4With at least one in Si/C nanofiber composite；Described Si/C Nanofiber composite is the surface that silicon is attached to carbon；The average grain diameter of described graphite is 1.5-12 micron；Described nanometer CoFe2O4, nanometer Fe1.5Ti0.5O3, nanometer Li2FeSiO4Average grain diameter be respectively 50-200 nanometer；Described Si/C nanometer A diameter of 50-200 nanometer of fibre composites.
2. according to the negative electrode active material described in claim 1, it is characterised in that: graphite and adding in described negative electrode active material The mass ratio adding agent is 100:1-20.
3. according to the negative electrode active material described in claim 2, it is characterised in that: graphite and adding in described negative electrode active material The mass ratio adding agent is 100:8-12.
4. a negative plate, it is characterised in that: this negative plate includes negative current collector and is coated on the negative of negative pole currect collecting surface Pole material；Described negative material includes negative electrode active material, conductive agent and binding agent；Described negative electrode active material is claim Negative electrode active material described in 1-3 any one.
Negative plate the most according to claim 4, it is characterised in that: the dressing thickness of described negative plate is graphite average grain diameter 2-3 times.
6. according to the negative plate described in claim 4, it is characterised in that: the compacted density of described negative plate is 0.6-1.3 g/ cm3。
7. a pulse buffer cell, it is characterised in that described pulse buffer cell includes cover plate, housing, battery core And electrolyte, described battery core and electrolyte is sealed in battery container, and described cover plate is hermetically connected with the shell；Described battery core includes Positive plate, negative plate and the barrier film being arranged between positive plate and negative plate；Wherein, described negative plate is claim 4-6 Negative plate described in any one.
8. a pulse buffer battery pack, it is characterised in that described pulse buffer battery pack is that the pulse described in claim 7 is delayed Rush cells in series to form.
9. a power battery module, it is characterised in that described module includes power battery pack and the pulse buffer battery of parallel connection Group；The both end voltage of described power battery pack is equal with the both end voltage of pulse buffer battery pack；Described pulse buffer battery pack For the pulse buffer battery pack described in claim 8.
CN201310035918.5A 2013-01-30 2013-01-30 A kind of negative electrode active material, negative plate and pulse buffer cell, battery pack and power battery module containing this negative plate Active CN103972507B (en)

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