CN104319426B - The method that the capacity of lithium ion battery is managed - Google Patents
The method that the capacity of lithium ion battery is managed Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 150
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000011258 core-shell material Substances 0.000 claims abstract description 141
- 230000008569 process Effects 0.000 claims abstract description 26
- 230000008859 change Effects 0.000 claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 40
- 239000007774 positive electrode material Substances 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 21
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical compound [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 claims description 19
- 229910002804 graphite Inorganic materials 0.000 claims description 16
- 239000010439 graphite Substances 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 238000007599 discharging Methods 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 abstract description 14
- 239000000126 substance Substances 0.000 description 13
- 229910052493 LiFePO4 Inorganic materials 0.000 description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 238000012937 correction Methods 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 239000011572 manganese Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000013528 artificial neural network Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- -1 lithium titanate Chemical class 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910009866 Ti5O12 Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000009191 jumping Effects 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M2010/4292—Aspects relating to capacity ratio of electrodes/electrolyte or anode/cathode
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A kind of method that the capacity of lithium ion battery is managed, including adding another negative active core-shell material from this first negative active core-shell material with different voltage platform in this lithium ion battery first negative active core-shell material, the negative active core-shell material making this lithium ion battery has two voltage platforms, this lithium ion battery two voltage platforms in discharge process can produce a violent pressure reduction change when changing, position and the electric discharge residual capacity of this lithium ion battery that the change of this pressure reduction occurs have a corresponding relation, thus can by detect this pressure reduction change determine whether this lithium ion battery reaches corresponding electric discharge residual capacity。
Description
Technical field
The present invention relates to lithium ion battery management domain, be specifically related to a kind of method that the capacity of lithium ion battery is managed。
Background technology
Battery remaining power, also known as one of important parameter that the state-of-charge (StateofCharge, SOC) of battery is battery status, can manage for the control of electric automobile and provide foundation。Ensure that SOC maintains in rational scope, it is prevented that overcharge or cross the damage of battery of being rivals in a contest, us can be made to be more reasonably utilized battery, improve the service life of battery, give full play to the power performance of battery system, reduce the cost that battery system is safeguarded。
Current battery SOC estimates that strategy mainly has: open-circuit voltage method, ampere-hour meter are mensuration, fuzzy neural network method and Kalman filtering method。Fuzzy neural network method and Kalman filtering method need battery data is analyzed and modeling, method is complex, and the Maturity of the hardware limitation and algorithm self owing to being subject to battery management system, most achievement also rest on the computer artificial result stage both at home and abroad at present, also have with a certain distance from concrete practical application。The current common method that battery SOC is estimated remains simple and effective open-circuit voltage method and ampere-hour meter is mensuration。
Open-circuit voltage method is the monotonic relationshi of open-circuit voltage and the SOC utilizing battery, by setting up the relation curve between residual capacity (SOC)-open-circuit voltage (OCV), open-circuit voltage values according to detecting determines SOC value, but SOC-OCV relation is measured strict by this method, it is only applicable to SOC and changes obvious battery with OCV, and current be representative with LiFePO4 lithium ion battery owing to having very smooth charge and discharge platform, SOC-OCV is relatively flat, therefore be not suitable for using open-circuit voltage method that SOC is estimated, even if the SOC-OCV curve of lithium ion battery is enough precipitous, if but absolute voltage is measured inaccurate, also the judgement to SOV can be affected。Ampere-hour meter is mensuration is, in battery system operation process, to the time, the charging and discharging currents of battery is integrated computing; then the dynamic SOC value of battery is estimated; but ampere-hour meter is mensuration higher to current sample required precision; therefore ampere-hour meter is mensuration actually at present exists certain error; and along with the increase of the time of use; cumulative error can be increasing; therefore when actually used; often SOC-OCV curve can be utilized to be modified ampere-hour meter is mensuration in conjunction with open-circuit voltage method, but the correction that ampere-hour meter is mensuration is had little significance by the flatter SOC-OCV curve of lithium ion battery。Therefore, how lithium ion battery residual capacity is monitored and management is still one of current urgent need to solve the problem。
Summary of the invention
In view of this, a kind of method that the capacity of lithium ion battery can be carried out effectively monitoring and management of necessary offer。
A kind of method that the capacity of lithium ion battery is managed, including:
Presetting lithium ion battery warning capacity in discharge process is D, 0 < D < 100%；
One first negative active core-shell material and one second negative active core-shell material are mixed to get the 3rd negative active core-shell material, the 3rd negative active core-shell material and a positive electrode active materials is used to prepare described lithium ion battery, this first negative active core-shell material will not change crystalline structure each other after mixing with this second negative active core-shell material, and this first negative active core-shell material to lithium current potential lower than this second negative active core-shell material to lithium current potential, specific capacity respectively MmAh/g and NmAh/g of this first negative active core-shell material and this second negative active core-shell material, this second negative active core-shell material mass percent x shared by described 3rd negative active core-shell material is (k1-D) M/ [(k1-D) M+DN], k1 is calibration factor, k1 is constant, 0.9 < k1 < 1.1；And
The discharge platform of described positive electrode active materials is V0, the charging platform of described first negative active core-shell material is V11～V12, the charging platform of described second negative active core-shell material is V21～V22, V21 is more than V12, this lithium ion battery is carried out multiplying power discharging, the voltage in discharge process of described lithium ion battery is monitored, when the voltage of described lithium ion battery falls into the scope of (V0-V21)～(V0-V12), the electric discharge residual capacity sending this lithium ion battery has reached the warning of D。
The way that capacity of lithium ion battery is managed provided by the invention, not only simply, conveniently, easily operate, and solve lithium ion battery and cross that gentle absolute voltage is measured inaccurate and the SOC that brings measures inaccurate problem due to voltage platform, it is possible to the capacity of lithium ion battery is carried out effectively monitoring and management。
Accompanying drawing explanation
Fig. 1 is the curve synoptic diagram of first embodiment of the invention the first lithium ion battery multiplying power discharging。
Fig. 2 a is the discharge curve of LiFePO4 half-cell, the charging curve of the half-cell of the 3rd negative active core-shell material that Fig. 2 b is graphite and phosphorus-carbon composite is mixed to form, Fig. 2 c is deducted, by the voltage of Fig. 2 a, the full battery discharge curve that the voltage of Fig. 2 b obtains, and Fig. 2 d is the discharge curve of the full battery of actual measurement。
Fig. 3 is the curve synoptic diagram of second embodiment of the invention the second lithium ion battery multiplying power charging。
Fig. 4 a is the charging curve of LiFePO4 half-cell, the discharge curve of the half-cell of the 3rd negative active core-shell material that Fig. 4 b is graphite and phosphorus-carbon composite is mixed to form, Fig. 4 c is deducted, by the voltage of Fig. 4 a, the full battery charging curve that the voltage of Fig. 4 b obtains, and Fig. 4 d is the charging curve of the full battery of actual measurement。
Fig. 5 is the multiplying power charging curve test figure of the 3rd negative active core-shell material half-cell of the different x value of the embodiment of the present invention 1。
Detailed description of the invention
First embodiment of the invention provides a kind of method that the capacity of lithium ion battery is managed, including:
S11, presetting first lithium ion battery warning capacity in discharge process is D, 0 < D < 100%；
S12, one first negative active core-shell material and one second negative active core-shell material are mixed to get the 3rd negative active core-shell material, the 3rd negative active core-shell material and a positive electrode active materials is used to prepare described first lithium ion battery, this first negative active core-shell material will not change crystalline structure each other after mixing with this second negative active core-shell material, and this first negative active core-shell material to lithium current potential lower than this second negative active core-shell material to lithium current potential, specific capacity respectively MmAh/g and NmAh/g of this first negative active core-shell material and this second negative active core-shell material, mass percent x=(k1-D) M/ [(k1-D) M+DN] that this second negative active core-shell material is shared in described 3rd negative active core-shell material；
S13, the discharge platform of described positive electrode active materials is V0, the charging platform of described first negative active core-shell material is V11～V12, the charging platform of described second negative active core-shell material is V21～V22, V21 is more than V12, this first lithium ion battery is carried out multiplying power discharging, the voltage in discharge process of described first lithium ion battery is monitored, when voltage falls into the scope of (V0-V21)～(V0-V12), the electric discharge residual capacity sending this first lithium ion battery has reached the warning of D。
In step s 11, can according to actual needs D be configured, for instance when this first lithium ion battery was carried out putting control by needs, D may be configured as 50% to 95%。
In step s 12, this positive electrode active materials is the one in the LiMn2O4 of the spinel structure of undoped p or doping, layered lithium manganate, lithium nickelate, cobalt acid lithium, LiFePO4, Li, Ni, Mn oxide or lithium nickel cobalt manganese oxide。Specifically, the LiMn2O4 of this spinel structure can by chemical formula LimMn2-nLnO4Representing, this lithium nickelate can by chemical formula LimNi1-nLnO2Representing, the chemical formula of this cobalt acid lithium can by LimCo1-nLnO2Representing, the chemical formula of this layered lithium manganate can by LimMn1-nLnO2, the chemical formula of this LiFePO4 can by LimFe1-nLnPO4Representing, the chemical formula of this Li, Ni, Mn oxide can by LimNi0.5+z-aMn1.5-z-bLaRbO4Representing, the chemical formula of this lithium nickel cobalt manganese oxide can by LimNicCodMneLfO2Represent, wherein 0.1≤m≤1.1,0≤n < 1,0≤z < 1.5,0≤a-z < 0.5,0≤b+z < 1.5,0 < c < 1,0 < d < 1,0 < e < 1,0≤f≤0.2, c+d+e+f=1。L and R is selected from one or more in alkali metal, alkali earth metal, the 13rd race's element, the 14th race's element, transition element and rare earth element, preferably, L and R at least one in Mn, Ni, Cr, Co, V, Ti, Al, Fe, Ga, Nd and Mg。
Described first negative active core-shell material or described second negative active core-shell material can be the one in graphite, lithium titanate, titanium dioxide or phosphorus-carbon composite。This lithium titanate is the lithium titanate of the lithium titanate of undoped or doping, and the lithium titanate of this undoped or the lithium titanate of doping have spinel structure。Specifically, the chemical formula of the lithium titanate of this undoped is Li4Ti5O12；The chemical formula Li of the lithium titanate of this doping(4-g)AgTi5O12Or Li4AhTi(5-h)O12Represent, wherein 0 < g≤0.33, and 0 < h≤0.5, A is selected from one or more in alkali metal, alkali earth metal, the 13rd race's element, the 14th race's element, transition element and rare earth element, it is preferred at least one in Mn, Ni, Cr, Co, V, Al, Fe, Ga, Nd, Nb and Mg。This phosphorus-carbon composite be will phosphorus distil after the phosphorus composite material of electrochemical reversible lithium storage that is adsorbed in the hole of porous carbon materials to be formed, phosphorus in this phosphorus-carbon composite is for reversible electrochemical storage lithium, porose material with carbon element is for improving the chemical property of phosphorus, and this phosphorus-carbon composite has higher specific capacity and good electric conductivity。
The positive electrode active materials related in the present invention or the charge/discharge platform of negative active core-shell material refer to the voltage platform that this positive electrode active materials or negative active core-shell material and lithium sheet composition half-cell show when carrying out charge/discharge。When a kind of positive electrode active materials or negative active core-shell material carry out charge/discharge in the half-cell of its composition, its voltage to experience three states, i.e. rise/fall-relatively steadily-rise/fall, in the these three stage, the relative stage of stable development is the longest, and stage is exactly the charge/discharge platform of this positive electrode active materials or negative active core-shell material relatively smoothly for this。Namely this positive electrode active materials or negative active core-shell material are in the half-cell of its composition during charge/discharge, its charge/discharge curve there will be two scope discontinuity, the charge/discharge curve relatively smoothly being between the two scope discontinuity is defined as the charge/discharge platform of this positive electrode active materials or negative active core-shell material, and said two scope discontinuity is as the starting point of this charge/discharge platform and terminal。
In step s 13, the discharge platform V0 of described positive electrode active materials refers to the intermediate value of the magnitude of voltage in the discharge curve of the half-cell of this positive electrode active materials and lithium sheet composition corresponding to two scope discontinuity。Owing to general positive electrode active materials is respectively provided with long and stable charge and discharge platform, the discharge platform of described positive electrode active materials therefore can be represented with above-mentioned intermediate value。The magnitude of voltage corresponding to beginning and end of V11 and the V12 respectively charging platform of described first negative active core-shell material。The magnitude of voltage corresponding to beginning and end of V21 and V22 respectively described second negative active core-shell material charging platform。
Refer to Fig. 1, in the discharge process of described first lithium ion battery, the first negative active core-shell material that lithium current potential is low is first discharged (referring to E to H section in Fig. 1), after the described first basic discharge off of negative active core-shell material, the second negative active core-shell material that lithium current potential is high is started electric discharge (referring to H to L section in Fig. 1)。When described first negative active core-shell material stops electric discharge, when described second negative active core-shell material starts to discharge (the H point in corresponding diagram 1), the electric discharge residual capacity of this first lithium ion battery is default D。
Owing to negative active core-shell material is at half-cell charging process its discharge process in full battery corresponding, and this negative active core-shell material is in half-cell discharge process its charging process in full battery corresponding, therefore, when a kind of positive electrode active materials discharges with a kind of negative active core-shell material full battery of composition, the charging curve of the discharge curve of this full battery and the discharge curve of this positive electrode active materials and this negative active core-shell material has obvious matching relationship；When a kind of positive electrode active materials is charged with a kind of negative active core-shell material full battery of composition, the discharge curve of the charging curve of this full battery and the charging curve of this positive electrode active materials and this negative active core-shell material has obvious matching relationship；The voltage of this full battery should be two electrodes to lithium difference in voltage, and the intersection of two electrode voltage platforms is the part of this full battery stable discharging。
In the discharge curve of described first lithium ion battery, discharge platform corresponding to described first negative active core-shell material is F to G section, the starting point of discharge platform corresponding to F point and G point respectively described first negative active core-shell material and initial point, the voltage Vf of F point is (V0-V11), and the voltage Vg of G point is (V0-V12)；Discharge platform corresponding to described second negative active core-shell material is I to J section, the starting point of discharge platform corresponding to I point and J point respectively described second negative active core-shell material and initial point, the voltage Vi of I point is (V0-V21), and the voltage Vj of J point is (V0-V22)。Reach before and after D in described lithium-ion electric tank discharge residual capacity, the discharge curve of described first lithium ion battery shows as by F to G segment hopping I to J section, now the discharge curve of described first lithium ion battery there will be a violent pressure reduction change, the Vg that initial point is G point of this pressure reduction change, terminal is the Vi of I point, owing to the pressure reduction between G point to I point changes very violent, the slope of this section of discharge curve is very big, therefore any voltage value can be looked for have reached D instruction as this first lithium ion electric discharge residual capacity in the voltage range between Vi to Vg。
Due to voltage just corresponding when the voltage Vh of H point is described first lithium ion battery arrival default D value, certain error can be there is in the magnitude of voltage that therefore other except D point point is corresponding in G to I section as warning value, but owing to electrode material is in the terminal voltage effect at its electric discharge initial stage with electric discharge latter stage, G to I section slope of a curve is very precipitous, therefore this error is less, usually, this error is not over 5%。For this error less further, it is possible to the scope of (Vh-pVh)～(Vh+pVh) has arrived the warning scope of default D as this first lithium-ion electric tank discharge residual capacity, 0 < p < 10%。It is further preferable that warning can be sent when the magnitude of voltage of described first lithium ion battery is just for Vh。The present embodiment is using the intermediate value of voltage Vg and the I of the G point voltage Vi put as the magnitude of voltage Vh, i.e. Vh=(Vg+Vi)/2 of H point。
Additionally, the first negative active core-shell material that material is determined and the second negative active core-shell material, described in described 3rd negative active core-shell material, the mixed proportion of the first negative active core-shell material and the second negative active core-shell material is different, described first negative active core-shell material, the each self-corresponding magnitude of voltage of beginning and end of the discharge platform that the second negative active core-shell material is corresponding in described first lithium ion battery discharge process determines that constant, but the position that the pressure reduction change produced when jumping to discharge platform corresponding to described second negative active core-shell material from the discharge platform that described first negative active core-shell material is corresponding occurs is different, it is also different that above-mentioned pressure reduction changes this first lithium ion battery remaining capacity value in discharge process corresponding when occurring。Set described second negative active core-shell material mass percent in described 3rd negative active core-shell material as x, then described first negative active core-shell material mass percent in described 3rd negative active core-shell material is (1-x), when described first negative active core-shell material discharge off, theoretical discharge residual capacity Dt=(1-x) M/ [(1-x) M+xN] of this first lithium ion battery when described second negative active core-shell material starts to discharge, it is modified calculating electric discharge residual capacity D actual under this mixed proportion to this theoretical discharge residual capacity Dt with correction coefficient k1, then, D=k1Dt=k1 (1-x) M/ [(1-x) M+xN]。In step sl D value is carried out preset after, described second negative active core-shell material mixed proportion x=(k1-D) M/ [(k1-D) M+DN] in described 3rd negative active core-shell material can be calculated。Described correction coefficient k1 is a constant herein, 0.9 < k1 < 1.1, specifically can be set according to the material character of the both positive and negative polarity active material selected when preparing described first lithium ion battery。
Refer to Fig. 2, in one embodiment of the invention, described positive electrode active materials is LiFePO4, described first negative active core-shell material is graphite, described second negative active core-shell material is phosphorus-carbon composite, figure a is the discharge curve of described LiFePO4 half-cell, the charging curve of the half-cell of the 3rd negative active core-shell material that figure b is graphite and phosphorus-carbon composite is mixed to form, scheme the discharge curve of described first lithium ion battery that the voltage that c is the half-cell charging curve using the voltage of described LiFePO4 half-cell discharge curve to deduct described 3rd negative active core-shell material obtains, figure d is the discharge curve of described first lithium ion battery of actual measurement, as can be seen from Figure 2, figure c and figure d almost overlaps, therefore, in the present embodiment, set k1=1。
When the residual capacity of described first lithium ion battery reaches the D preset, battery management system can be sent warning, to carry out next step action, for instance now can stop described first lithium ion battery and proceed electric discharge and put preventing described first lithium ion battery from crossing。
Before described step S12, can farther including the step of a mensuration correction coefficient k1, in order to more accurately described first lithium ion battery electric discharge residual capacity in actual use to be managed, concrete steps include:
S21, in the identical situation of other conditions, sets x as different numerical value x1, x2, x3 x (n-1), and xn prepares described first lithium ion battery respectively, and 0 < x1 < 1,0 < x2 < 1,0 < x3 < 1,0 < x (n-1) < 1,0 < xn < 1；
S22, carries out multiplying power discharging to the plurality of first lithium ion battery, reading numerical value corresponding to following table from the discharge curve of the plurality of first lithium ion battery, row-column list of going forward side by side, and
| x | x1 | x2 | x3 | ··· | x(n-1) | xn |
| Vg | Vg1 | Vg2 | Vg3 | ··· | Vg(n-1) | Vgn |
| Vi | Vi1 | Vi2 | Vi3 | ··· | Vi(n-1) | Vin |
| Vh | Vh1 | Vh2 | Vh3 | ··· | Vh(n-1) | Vhn |
| D | D1 | D2 | D3 | ··· | D(n-1) | Dn |
| Dt | Dt1 | Dt2 | Dt3 | ··· | Dt(n-1) | Dtn |
| D/Dt | D1/Dt1 | D2/Dt2 | D3/Dt3 | ··· | D(n-1)/Dt(n-1) | Dn/Dtn |
S23, calculates k1, k1=[D1/Dt1+D2/Dt2+D3/Dt3+D (n-1)/Dt (n-1)+Dn/Dtn]/n。
In step s 12, x=(k1-D) M/ [(k1-D) M+DN] can be calculated according to the k1 obtained in default D value and step 23, prepare described first lithium ion battery further according to x value。
Further, after calculating k1, also further with the data of upper table, Vg, Vi and Vh can be corrected, respectively obtain the Vg after correctionFlat、ViFlatAnd VhFlat。Wherein, VgFlat=[Vg1+Vg2+Vg3+Vg (n-1)+Vgn]/n, ViFlat=[Vi1+Vi2+Vi3+Vi (n-1)+Vin]/n, VhFlat=[Vh1+Vh2+Vh3+Vh (n-1)+Vhn]/n。
In step s 13, the voltage in discharge process of described first lithium ion battery is monitored, when voltage falls into VgFlat～ViFlatScope time, the electric discharge residual capacity sending this first lithium ion battery has reached the warning of D。Preferably, when the voltage of described first lithium ion battery falls into (VhFlat-pVhFlat)～(VhFlat+pVhFlat) scope time send warning, 0 < p < 10%。It is further preferable that the magnitude of voltage at described first lithium ion battery is just VhFlatTime send warning。
Second embodiment of the invention provides a kind of method that the charging capacity of lithium ion battery is managed, including:
S31, presetting second lithium ion battery warning capacity in charging process is C, 0 < C < 100%；
S32, described first negative active core-shell material and one the 4th negative active core-shell material are mixed to get the 5th negative active core-shell material, the 5th negative active core-shell material and described positive electrode active materials is used to prepare described second lithium ion battery, this first negative active core-shell material will not change crystalline structure each other after mixing with the 4th negative active core-shell material, and this first negative active core-shell material to lithium current potential higher than the 4th negative active core-shell material to lithium current potential, the specific capacity respectively ZmAh/g of the 4th negative active core-shell material, mass percent y=(k2-C) M/ [(k2-C) M+CZ] that 4th negative active core-shell material is shared in described 5th negative active core-shell material；
S33, the charging platform of described positive electrode active materials is V5, the discharge platform of described first negative active core-shell material is V31～V32, the discharge platform of described 4th negative active core-shell material is V41～V42, V32 is more than V41, this second lithium ion battery is carried out multiplying power charging, the voltage in charging process of described second lithium ion battery is monitored, when voltage falls into the scope of (V5-V32)～(V5-V41), the charging capacity sending this lithium ion battery has reached the warning of C。
Described 4th negative active core-shell material can be the one in graphite, lithium titanate, titanium dioxide or phosphorus-carbon composite。This lithium titanate is the lithium titanate of the lithium titanate of undoped or doping, and the lithium titanate of this undoped or the lithium titanate of doping have spinel structure。Specifically, the chemical formula of the lithium titanate of this undoped is Li4Ti5O12；Chemical formula Li (4-g) AgTi5O12 or Li4AhTi (5-h) O12 of the lithium titanate of this doping represents, wherein 0 < g≤0.33, and 0 < h≤0.5, A is selected from one or more in alkali metal, alkali earth metal, the 13rd race's element, the 14th race's element, transition element and rare earth element, it is preferred at least one in Mn, Ni, Cr, Co, V, Al, Fe, Ga, Nd, Nb and Mg。This phosphorus-carbon composite is the phosphorus composite material of the electrochemical reversible lithium storage formed at porose carbon material surface In-situ reaction by the mode adsorbed by the phosphorus of distillation, phosphorus in this phosphorus-carbon composite is for reversible electrochemical storage lithium, and porose material with carbon element is for improving the chemical property of phosphorus。
Second embodiment of the invention is essentially identical with the method for first embodiment, it is different in that, described first negative active core-shell material to lithium current potential higher than described 4th negative active core-shell material to lithium current potential, refer to Fig. 3, in the charging process of described second lithium ion battery, first the first negative active core-shell material that lithium current potential is high is charged (referring to O to R section in Fig. 1), after described first negative active core-shell material is charged substantially, the 4th negative active core-shell material that lithium current potential is low is started to charge up (referring to R to U section in Fig. 1)。When described first negative active core-shell material charging is complete, starting during to described 4th negative active core-shell material charging (the R point in corresponding diagram 1), the charging capacity of this second lithium ion battery is default C。
In the charging curve of described second lithium ion battery, charging platform corresponding to described first negative active core-shell material is P to Q section, the beginning and end of P point and Q point respectively charging platform corresponding to described first negative active core-shell material, the voltage Vp of P point is (V5-V31), and the voltage Vq of Q point is (V5-V32)；Charging platform corresponding to described 4th negative active core-shell material is S to T section, the beginning and end of S point and T point respectively charging platform corresponding to described 4th negative active core-shell material, the voltage Vs of S point is (V5-V41), and the voltage Vf of F point is (V5-V42)。Reach before and after C in described lithium ion battery charging capacity, the charging curve of described second lithium ion battery shows as by P to R segment hopping S to T section, now the charging curve of described first lithium ion battery there will be a violent pressure reduction change, namely the Vs of S point is jumped to by the Vq of Q point, owing to the pressure reduction between Q point to S point changes very violent, the slope of this section of charging curve is very big, therefore any voltage value can be looked for have reached C instruction as this second lithium ion charging capacity in the voltage range between Q point to S point。
Voltage corresponding to R point is that described second lithium ion battery arrives voltage just corresponding when presetting C value, certain error can be there is in the magnitude of voltage that therefore other except R point point is corresponding in Q to S section as warning value, but owing to electrode material is in the terminal voltage effect at its charging initial stage with charging latter stage, the voltage slope of Q to S section is very precipitous, therefore this error is less, usually, this error is not over 5%。For this error less further, it is possible to arrived the warning scope of default C using the scope of (Vr-pVr)～(Vr+pVr) as this second lithium ion battery charging capacity, 0 < p < 10%。It is further preferable that warning can be sent when the magnitude of voltage of described first lithium ion battery is just for Vr。In the present embodiment, using the intermediate value of voltage Vq and the S of the Q point voltage Vs put as the magnitude of voltage Vr, i.e. Vr=(Vq+Vs)/2 of R point。
Set described 4th negative active core-shell material mass percent in described 5th negative active core-shell material as y, then described first negative active core-shell material mass percent in described 5th negative active core-shell material is (1-y), when described first negative active core-shell material charging is complete, when described 4th negative active core-shell material is started to charge up, theoretical charging capacity Ct=(1-y) M/ [(1-y) M+yZ] of this second lithium ion battery, it is modified calculating charging capacity C actual under this mixed proportion to this theory charging capacity Ct with k2 value, then, C=k2Ct=k2 (1-y) M/ [(1-y) M+xZ]。In step sl C value is carried out preset after, described second negative active core-shell material mixed proportion y=(k2-C) M/ [(k2-C) M+CZ] in described 5th negative active core-shell material can be calculated。Described correction coefficient k2 is a constant herein, 0.9 < k2 < 1.1, specifically can be set according to the material character of the both positive and negative polarity active material selected when preparing described second lithium ion battery。
Refer to Fig. 4, in one embodiment of the invention, using LiFePO4 as positive electrode active materials, using phosphorus-carbon composite as the first negative active core-shell material, using graphite as the 4th negative active core-shell material, figure a is the charging curve of described LiFePO4 half-cell, the discharge curve of the half-cell of the 5th active material that figure b is graphite and phosphorus-carbon composite is mixed to form, scheme the charging curve of described second lithium ion battery that the voltage that c is the half-cell discharge curve using the voltage of described LiFePO4 half-cell charging curve to deduct described 5th negative active core-shell material obtains, figure d is the charging curve of described second ion battery of actual measurement, figure c and figure d almost overlaps, therefore, in the present embodiment, set k2=1。
When the charging capacity of described second lithium ion battery reaches the C preset, battery management system can be sent warning, to carry out next step action, for instance now can stop described second lithium ion battery and proceed charging to prevent described second lithium ion battery from overcharging。
Before described step S32, can farther including the step of a mensuration correction coefficient k2, in order to more accurately described second lithium ion battery charging capacity in actual use to be managed, concrete steps include:
S41, in the identical situation of other conditions, sets y as different numerical value y1, y2, y3 y (n-1), and yn prepares described second lithium ion battery respectively, and 0 < y1 < 1,0 < y2 < 1,0 < y3 < 1,0 < y (n-1) < 1,0 < yn < 1；
S42, carries out multiplying power charging to the plurality of second lithium ion battery, reads the numerical value corresponding to following table from the charging curve of this institute the second lithium ion battery, row-column list of going forward side by side, and
| y | y1 | y2 | y3 | ··· | y(n-1) | yn |
| Vq | Vq1 | Vq2 | Vq3 | ··· | Vq(n-1) | Vqn |
| Vs | Vs1 | Vs2 | Vs3 | ··· | Vs(n-1) | Vsn |
| Vr | Vr1 | Vr2 | Vr3 | ··· | Vr(n-1) | Vrn |
| C | C1 | C2 | C3 | ··· | C(n-1) | Cn |
| Ct | Ct1 | Ct2 | Ct3 | ··· | Ct(n-1) | Ctn |
| C/Ct | C1/Ct1 | C2/Ct2 | C3/Ct3 | ··· | C(n-1)/Ct(n-1) | Cn/Ctn |
S43, calculates k2, k2=[C1/Ct1+C2/Ct2+C3/Ct3+C (n-1)/Ct (n-1)+Cn/Ctn]/n。
In step s 32, y=(k2-C) M/ [(k2-C) M+CZ] can be calculated according to the k2 obtained in default C value and step 23, prepare described second lithium ion battery further according to y value。
Further, after calculating k2, also further with the data of upper table, Vq, Vs and Vr can be corrected, respectively obtain the Vq after correctionFlat、VsFlatAnd VrFlat。Wherein, VqFlat=[Vq1+Vq2+Vq3+Vq (n-1)+Vqn]/n, VsFlat=[Vs1+Vs2+Vs3+Vs (n-1)+Vsn]/n, VrFlat=[Vr1+Vr2+Vr3+Vr (n-1)+Vrn]/n。
In step S33, the voltage in charging process of described second lithium ion battery is monitored, when voltage falls into VqFlat～VsFlatScope time, the charging capacity sending this second lithium ion battery has reached the warning of C。Preferably, when the voltage of described second lithium ion battery falls into (VrFlat-pVrFlat)～(VrFlat+pVrFlat) scope time send warning, 0 < p < 10%。It is further preferable that the magnitude of voltage at described second lithium ion battery is just VrFlatTime send warning。
Embodiment 1
The graphite of different mixing proportion, phosphorus-carbon composite are mixed with lithium ion half-cell, and the preparation method of this lithium ion half-cell is as follows:
(1) graphite, phosphorus-carbon composite (phosphorous 40%), acetylene black are weighed, add PVDF (to dissolve with N-Methyl pyrrolidone, mass fraction 10%), make graphite+P-C material: acetylene black: PVDF=7:2:1 (mass ratio), add N-Methyl pyrrolidone and make viscosity suitably (graphite, P-C material, acetylene black, PVDF total amount 0.5g add N-Methyl pyrrolidone and be about 1.5mL)。Pour ground and mixed in mortar into。
(2) Copper Foil is taken, surface is clean by alcohol wipe, glue on a glass。Treat that copper foil surface is dried, the mixed liquor in mortar is poured on Copper Foil one end, carries out blade coating。
(3) put into 60 DEG C of oven for drying 24h by scraping the Copper Foil coated, take out Copper Foil, punching, pole piece is put into vacuum drying oven 60 DEG C and dries 24h。
(4) use the pole piece dried with lithium sheet as the two poles of the earth, with LBC305-01 as electrolyte, make button cell, obtain lithium ion half-cell。
After obtaining lithium ion half-cell, calculating for standard specific volume gauge with 350mAh/g, carry out multiplying power charging with 0.1C, the charging curve of the lithium ion half-cell of this different mixing proportion is as shown in Figure 3, the numerical value corresponding to following table, row-column list of going forward side by side is read from the charging curve of this first lithium ion battery。
| x | 0 | 10% | 20% | 29% | 100% |
| Vg | 0.25V | 0.25V | 0.25V | 0.25V | -- |
| Vi | -- | 0.75V | 0.75V | 0.75V | 0.75V |
| Vh | -- | 0.5V | 0.5V | 0.5V | -- |
| D | -- | 302/400=75.5% | 265/421=62.9% | 253/530=47.7% | -- |
| Dt | -- | 315/419=75.1% | 280/488=57.4% | 249/550=45.3% | -- |
| D/Dt | -- | 1.005 | 1.096 | 1.053 | -- |
Calculate k1=(1.005+1.096+1.053)/4=1.051, VhFlat=0.5V。
The charging curve of this lithium ion half-cell correspond to the discharge curve of the full battery of lithium ion being mixed with by graphite, phosphorus-carbon composite。The electric discharge residual capacity presetting the full battery of described lithium ion stops electric discharge when being 90% thus controlling this lithium ion battery and crossing and put, the theoretical capacity of graphite is 350mAh/g, the theoretical capacity of phosphorus-carbon composite (phosphorous 40%) is 1038mAh/g, calculating graphite mass percent in the 3rd negative active core-shell material is 95.5%, phosphorus-carbon composite mass percent in the 3rd negative active core-shell material is 4.5%, prepares the full battery of lithium ion according to aforementioned proportion。This lithium ion full battery voltage in discharge process is monitored, when the voltage of described lithium ion battery falls into (3.45V-0.5V × 110%) to (3.45V-0.5V × 90%), namely, during 2.9V to 3.00V, the full battery of this lithium ion is made to stop electric discharge。
The present invention adds another negative active core-shell material from this first negative active core-shell material with different voltage platform in lithium ion battery the first negative active core-shell material, the negative active core-shell material making this lithium ion battery has two voltage platforms, this lithium ion battery two voltage platforms in charge and discharge process can produce a violent pressure reduction change when changing, position and electric discharge residual capacity or the charging capacity of this lithium ion battery that the change of this pressure reduction occurs have a corresponding relation, thus can by detect this pressure reduction change determine whether this lithium ion battery reaches corresponding electric discharge residual capacity or charging capacity。Additionally, be also with this pressure reduction change occur position and electric discharge residual capacity or the charging capacity of this lithium ion battery between corresponding relation be modified ampere-hour meter is mensuration。
The way that capacity of lithium ion battery is managed provided by the invention, not only simply, conveniently, easily operate, and solve lithium ion battery and cross that gentle absolute voltage is measured inaccurate and the SOC that brings measures inaccurate problem due to voltage platform, it is possible to the capacity of lithium ion battery is carried out effectively monitoring and management。
It addition, those skilled in the art can also do other change in spirit of the present invention, certainly, these changes done according to present invention spirit, all should be included within present invention scope required for protection。
Claims (9)
1. the method capacity of lithium ion battery being managed, including:
Presetting lithium ion battery warning capacity in discharge process is D, 0 < D < 100%；
One first negative active core-shell material and one second negative active core-shell material are mixed to get the 3rd negative active core-shell material, the 3rd negative active core-shell material and a positive electrode active materials is used to prepare described lithium ion battery, this first negative active core-shell material will not change crystalline structure each other after mixing with this second negative active core-shell material, and this first negative active core-shell material to lithium current potential lower than this second negative active core-shell material to lithium current potential, specific capacity respectively MmAh/g and NmAh/g of this first negative active core-shell material and this second negative active core-shell material, this second negative active core-shell material mass percent x shared by described 3rd negative active core-shell material is (k1-D) M/ [(k1-D) M+DN], k1 is calibration factor, k1 is constant, 0.9 < k1 < 1.1 and k1 > D；And
The discharge platform of described positive electrode active materials is V0, the charging platform of described first negative active core-shell material is V11～V12, the charging platform of described second negative active core-shell material is V21～V22, V21 is more than V12, this lithium ion battery is carried out multiplying power discharging, the voltage in discharge process of described lithium ion battery is monitored, when the voltage of described lithium ion battery falls into the scope of (V0-V21)～(V0-V12), the electric discharge residual capacity sending this lithium ion battery has reached the warning of D。
2. the method that the capacity of lithium ion battery is managed as claimed in claim 1, it is characterized in that, the electric discharge residual capacity sending this lithium ion battery when described lithium ion battery voltage in discharge process falls into the scope of (Vh-pVh)～(Vh+pVh) has reached the warning of D, wherein, Vh=(V0-V21+V0-V12)/2,0 < p < 10%。
3. the method that the capacity of lithium ion battery is managed as claimed in claim 1, it is characterized in that, when the voltage of described lithium ion battery is Vh, the electric discharge residual capacity sending this lithium ion battery has reached the warning of D, wherein, Vh=(V0-V21+V0-V12)/2。
4. the method that the capacity of lithium ion battery is managed as claimed in claim 1, it is characterised in that described first negative active core-shell material or described second negative active core-shell material are the one in graphite, lithium titanate, titanium dioxide or phosphorus-carbon composite。
5. the method that the capacity of lithium ion battery is managed as claimed in claim 1, it is characterised in that farther include the step of a described calibration factor k1 of mensuration, including:
In the identical situation of other conditions, setting x as different numerical value x1, x2, x3 x (n-1), xn prepares described lithium ion battery respectively, and 0 < x1 < 1,0 < x2 < 1,0 < x3 < 1,0 < x (n-1) < 1,0 < xn < 1；
Multiple described lithium ion batteries are carried out multiplying power discharging, read from the discharge curve of these lithium ion batteries multiple and calculating numerical value corresponding to following table, row-column list of going forward side by side,
Wherein Vg is the magnitude of voltage of the terminal of the discharge platform that described first negative active core-shell material is corresponding on the discharge curve of described lithium ion battery, Vi is the magnitude of voltage of the initial point of the discharge platform that described second negative active core-shell material is corresponding on the discharge curve of described lithium ion battery, Vh=(Vg+Vi)/2, D is electric discharge residual capacity corresponding for voltage Vh on the discharge curve of described first lithium ion battery, Dt is the theoretical residual capacity that described x is corresponding, Dt=(1-x) M/ [(1-x) M+xN], and
Calculate k1, k1=[D1/Dt1+D2/Dt2+D3/Dt3+D (n-1)/Dt (n-1)+Dn/Dtn]/n。
6. the as claimed in claim 5 method that the capacity of lithium ion battery is managed, it is characterised in that farther include the step that a pair Vg, Vi and Vh are corrected, respectively obtain Vg after Vg, Vi and Vh are correctedFlat、ViFlatAnd VhFlat, VgFlat=[Vg1+Vg2+Vg3+Vg (n-1)+Vgn]/n, ViFlat=[Vi1+Vi2+Vi3+Vi (n-1)+Vin]/n, VhFlat=[Vh1+Vh2+Vh3+Vh (n-1)+Vhn]/n。
7. the method that the capacity of lithium ion battery is managed as claimed in claim 6, it is characterised in that the voltage in discharge process of described lithium ion battery is monitored, when the voltage of described lithium ion battery falls into ViFlat～VgFlatScope time, the electric discharge residual capacity sending this lithium ion battery has reached the warning of D。
8. the as claimed in claim 6 method that the capacity of lithium ion battery is managed, it is characterised in that described lithium ion battery voltage in discharge process is monitored, when the voltage of described lithium ion battery falls into (VhFlat-pVhFlat)～(VhFlat+pVhFlat) scope time, the electric discharge residual capacity sending this lithium ion battery has reached the warning of D, 0 < p < 10%。
9. the method that the capacity of lithium ion battery is managed as claimed in claim 6, it is characterised in that the voltage in discharge process of described lithium ion battery is monitored, when the magnitude of voltage of described lithium ion battery is just VhFlatTime, the electric discharge residual capacity sending this lithium ion battery has reached the warning of D。
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