Journal of Power Sources 274 (2015) 957e964

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Journal of Power Sources

journal homepage: www.elsevier.com/locate/jpowsour

Optimal charging method for lithium ion batteries using a universal

voltage protocol accommodating aging
Zhen Guo a, Bor Yann Liaw b, *, Xinping Qiu c, Lanlan Gao d, Changshui Zhang a, *
a
State Key Laboratory of Intelligent Technologies and Systems, Tsinghua National Laboratory for Information Science and Technology (TNList), Department
of Automation, Tsinghua University, Beijing 100084, China
b
Hawaii Natural Energy Institute, SOEST, University of Hawaii at Manoa, Honolulu, HI 96822, USA
c
Key Laboratory of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, China
d
China Institute of Electronic System Engineering Company, Beijing 100141, China

h i g h l i g h t s

A fast charging technique using a universal charging protocol that is independent of cell aging.

A fast charging technique that has great tolerance to cell variability.

A fast charging technique that is constrained by charging time.

Prolong cell cycle life, and retain high charging efficiency, while keep short charging time.

Easy for implementation in practical applications.

a r t i c l e i n f o a b s t r a c t

Article history: An effective optimum charging technique for lithium ion batteries using a universal voltage protocol
Received 19 August 2014 (UVP) that can accommodate cell aging is presented here. This charging method demands less learning to
Received in revised form varying state-of-health (SOH) conditions with potential to improve charging efficiency and cycle life. The
22 October 2014
simplicity of UVP makes the implementation easier than the conventional constant currenteconstant
Accepted 29 October 2014
voltage (CCeCV)-based methods. Here, the mathematical formulation, optimization targets (e.g. minimal
Available online 30 October 2014
time) and constraints (terminal voltages and other instrumental and cell electrochemistry-limited ones)
are explained from the protocol design considerations. An equivalent circuit model was used and its
Keywords:
Optimum battery charging technique
parameters derived from the analysis of test data, which could yield a nonlinear varying current profile
Universal voltage protocol (UVP) (VCP) by simulation and a genetic algorithm-based optimization. Both UVP and VCP were used in the
Varying current profile (VCP) validation to illustrate better charging efficiency and capacity retention, which showed a much improved
State of health (SOH) cycle life.
Charging efficiency © 2014 Elsevier B.V. All rights reserved.
Cycle life

1. Introduction tracing battery performance and its attenuation with a fixed

Lithium ion batteries (LIBs) are remarkable energy storage sys-
tems for many applications. Compared to other battery chemistries,
LIBs are attractive for their high specific energy and high power
capability in performance. Nonetheless, the LIB performance at-
tenuates with charging and discharging protocols. In practical ap-
plications, most discharge conditions are multifarious, difficult to
assess their impacts on battery performance realistically in the
field. In contrast, the charging conditions are more convenient for
* Corresponding authors.
E-mail addresses: bliaw@hawaii.edu (B.Y. Liaw), zcs@mail.tsinghua.edu.cn
(C. Zhang).
charging protocol. The most commonly used charging protocol is a
constant-current (CC) process, often combined with a constant-
voltage (CV) trickle charge, to recharge a battery. In the CC step,
the galvanostatic control is used to facilitate coulomb counting for
state-of-charge (SOC) estimate. The introduction of the CV step is
primarily to prevent overcharging; thus, a current-tapering
charging is used to recharge the battery to full. In portable or mo-
bile applications, the needs for convenience in usage and mobility
drive the desire for fast charging, which require an optimum
charging protocol to shorten the charging time. At the same time, it
is also desirable to improve the charging efficiency, minimize any
performance attenuation, and sustain a safe operation of a LIB
system.

http://dx.doi.org/10.1016/j.jpowsour.2014.10.185
0378-7753/© 2014 Elsevier B.V. All rights reserved.
958 Z. Guo et al. / Journal of Power Sources 274 (2015) 957e964
A number of studies on optimizing charging processes and
optimization techniques for LIBs have been reported in the litera-
ture. Most of them were established on model-based simulations
that require multi-step current controls to achieve the goals [1e3].
These approaches can be exemplified by a variety of electro-
chemical models based on porous electrode theory-guided elec-
trochemical engineering approaches (e.g. PE-BEEM), often in an
‘averaged volume and mass’ framework, such as that in the single
particle models (SPM), that come with a large set of coupled
physical parameters in mass transport and electric field and use the
scheme of ‘balance of plant’ to derive reasonable optimization
constraints. Some others prefer empirically derived multi-step
diminishing currents (may up to four to five steps preset for
down selection) to perform optimum charging. Based on an opti-
mization scheme, a proper current level in each step shall be
determined by numerical algorithms or engineering methods using
algorithms based on ant colony system (ACS), fuzzy control (FC), or
Taguchi experimental design, in attempts to optimize current se-
lection [4e6]. The multi-step current charging methods are often
derived without full understanding of the mechanism involved in
the charging process, and their applications are often restricted by
certain subjective factors (e.g. initial current selection and the in-
telligence in algorithms or rules generation). There are other at-
tempts to improve the conventional CCeCV methods for better
charging results. Sikha et al. reported an empirical formula
described as ‘varying current decay’ (VCD) protocol to replace
CCeCV or purely CV charging for a LiCoO2-based LIB, attempting to
shorten the recharging time, while minimizing impacts on cycle life
[7]. They showed the comparison of charging results on the per-
formance of the cell as a function of cycle number with discussion
on the impacts of the fading behavior in the cell. Mechanistic
reasoning has been given for the need of a better protocol in fast
charging. Chen et al. used a gray-prediction algorithm to replace a
common CV mode float charging protocol and implemented the
algorithm into a LIB charging system [8]. These are just a couple of
examples to show the state-of-the-art in the fast and safe charging
protocol developments. Although improved in reducing charging
time and/or increasing charging efficiency, these prior attempts
could not effectively overcome the polarization increase over time
when batteries are aged and faded. There is an urgent need to
develop a more reliable charging protocol that can address aging
phenomena and be able to accommodate capacity fade (often
caused by active materials loss) or power fade (induced by
impedance increase over time). A more reliable charging protocol
should minimize fading-induced impacts on battery performance.
It should also reduce unwanted safety and reliability concerns, such
as overcharging, which often reduces battery life.
Here, an effective optimum charging method is proposed and
illustrated using a 2.2 Ah LiCoO2/LiNixMnyCozO2-based LS-18650
LIB cell to demonstrate its effectiveness. In this method, a univer-
sal voltage protocol (UVP) with less demanding of learning can be
obtained and applied to recharging the cell at various stages of
state-of-health (SOH) conditions. This UVP is based on a hypo-
thetical question, “if a universal charging protocol can be derived
that is independent of aging while provides the best efficiency to
recharge a battery to 100% SOC in a desired time frame?” If so, this
UVP method shall provide a better generalization and easier
implementation for charger control. On the other hand, the current
profile would vary as a function of SOC and SOH. Thus, this UVP
approach is also a unique technique using a varying current profile
(VCP) that is fundamentally different from the conventional VCD
protocols. Some other unique aspects of this approach include:
(1) An optimized UVP that is constrained by charging time. It is
important to note that in this work, the optimization scheme
uses charging time as an input parameter to derive the
optimal UVP first. The VCP was then deduced from the UVP,
which is substantially different from other schemes in the
prior arts. Inevitably, the VCP will be limited by the charger's
power capability. Without charger's power constraint, we
showed that the cell in the range of 80%e100% SOHs could be
fully recharged within an hour as programmed, whereas
other considerations such as charging efficiency, perfor-
mance retention (e.g. cycle life), and safety measures (e.g.
overcharge tolerance) were evaluated as well.
(2) Mathematical formulation with optimization goals (i.e.
reduced charging time) and constraints (terminal voltage,
charging protocols, etc.) are derived from the CCeCV
charging curves and data analysis, from which characteristic
parameters and functional coefficients required for an
equivalent circuit model (ECM) [9] were quantified using a
numerical regression and optimization algorithm.
(3) An alternative time-based nonlinear VCP strategy was
demonstrated to mitigate mass and charge transfer limita-
tions as an effective mean to improve charge efficiency while
reducing charging time. A practical transformation from
realistic test results to derive aging-affected VCPs via quan-
titative mathematical expressions is realized. This ability
makes this UVP/VCP approach capable of adopting cycle aging
and capacity fade into charging protocols for safe operation of
the charging process. This is the first time that SOH-
dependent charging protocol was developed successfully.
2. Background principles
2.1. State-of-the-art and issues
The CCeCV or CV floating charge protocols have been widely
used in the battery industry due to the simplicity, convenience, and
wide acceptance in their practices. For practical applications, there
is a strong desire to improve charging efficiency and reduce
charging time; yet, these protocols have limitations in achieving
such an objective while maintaining charge retention in LIBs. In the
CC step, as SOC increases, the polarization phenomenon shall
intensify, since mass transport and charge transfer become more
difficult. In some cases, lithium deposition (plating) in the negative
electrode emerges to cause capacity loss irreversibly and leaves the
cell to great risks of internal short and thermal runaway. To miti-
gate such risks, the CV step is employed to prevent overcharging;
yet, prolonging the charging time as a consequence. To reduce
charging time, higher rates are required, which decreases the
charging efficiency due to Joule heating. Therefore, to reduce
charging time, while improving charging efficiency, a better
charging methodology needs to be developed.
Fig. 1(a) shows a series of cell voltage vs. SOC curves in the CC step
at 0.2C, 0.5C, 1C, 2C, and 3C, respectively, for a typical fresh LS-18650
cell. In these experiments, the cut-off voltage at the end-of-charge
(VEOC) was 4.2 V, whereas the corresponding SOC (SOCEOC) in the
CC step could not reach 100% in each case. A heuristic idea was raised
to ask the question, ‘why fast charging to date could not reach the
fully charged state (ideally 100% SOC) within a manageable time?’ To
explore this possibility with intent to achieve the optimum charging
within an allotted time frame, without sacrificing cell performance,
as the solid line in Fig. 1(a) attempts to address; such a charging
protocol (conformed to the voltage vs. SOC profile as shown) could
be realized in the charging control to reach 100% SOC at the end-of-
charge (EOC) in a desired charging time and with better efficiency.
This is the optimum charging protocol we intend to achieve. Fig. 1(b)
shows the inverse relationship between charging time and charging
 Z. Guo et al. / Journal of Power Sources 274 (2015) 957e964
Fig. 1. (a) Charging profiles in the constant current (CC) step at 0.2C, 0.5C, 1C, 2C, and 3C, respectively, of a {LiCoO2 þ LiNixMnyCozO2} composite cathode-based LIB used in this work.
A desirable charging profile to reach 100% SOC without a constant voltage (CV) step is also shown. (b) The corresponding charging time for the CC step and the entire CCeCV
protocol as a function of C rate.
rate and the portion of charging time associated with the CC step in
the CCeCV protocol. As the rate increases, more time needs to spend
on CV step. One should also be aware of that after a certain rate the
benefit of time reduction from the increasing rate in the CC step
should diminish quickly by the lengthening of the charging time in
the CV step. Therefore, a varying current (VC) strategy as a function
of SOC and time must be adopted to shorten charging time, as
suggested in the heuristic idea. To test the water, the voltage
response as a function of VC shall be modeled first.
2.2. Varying current (VC) strategy
In general, the impedance of a cell shall change with SOC [10], as
shown in Fig. 2(a). The cell impedance shall increase toward the
end-of-discharge (EOD), as the ability in moving the residual
charge from one electrode to another in the cell becomes more
difficult. Although it is a common practice to reduce the current to
lower Joule heating in order to improve the charging efficiency,
disregarding resistance variations; the philosophy employed in this
work guides a hypothetical yet ideal current profile created ac-
cording to impedance response in the cell, as represented in
Fig. 2(b). In the beginning of charging from the EOD, as the resis-
tance rapidly varies with its value from high to low, the current
should increase sharply. The maximum current should follow the Li
ion transport in the electrolyte and through the porous electrode
architecture, where mass transport is usually the limiting factor for
electrochemical reactions. As the SOC increases, while the mass
transport becomes gradually constrained, the current should
reduce accordingly, as shown by a nonlinear VC profile with time t
in Fig. 2(b) and its functional formula can be expressed as:
iðtÞ ¼ at$expðbtÞ
Fig. 2. (a) The dc resistance as a function of SOC and (b) the charging current as a function of time for the proposed charging profile with a nonlinear varying-current curve.
959
where t is the charging time and a, b non-dimensional coefficients.
Practically, with specific start and finishing times (denoted as ti and
tf, respectively), the VC curve shall be determined by the co-
efficients a and b. The optimum charging protocol can be regarded
as how to obtain the appropriate a, b, ti, and tf through a certain
optimization method in a mathematical model.
2.3. Mathematical expressions
In the mathematical model, the charging time t can be set as an
optimization target as


mint ¼ tf  ti (2)
To assess the effectiveness of various charging protocols, some
constraints and variables that are related to battery performance
characteristics, such as SOC, capacity Q, heat generated by the
charging process q, and the terminal voltage U, should be consid-
ered as benchmarks for comparison. Ideally, the best quantities
should be retained in the improved charging protocol with the
following qualities, as expressed in the mathematical descriptions
as follows:
SOCtf ¼ SOCEOC (3)
q  qCCeCV (4)
Utf ¼ VEOC (5)
where SOCtf and Utf are the final SOC and cell voltage at the end of
(1) the charge regime in the experiments. Considering the uncertainty
in experimental measurements, the SOCtf could be retained within
960 Z. Guo et al. / Journal of Power Sources 274 (2015) 957e964

98%~100%, while the Utf in the range of 4.18 Ve4.20 V. qCCeCV de-
notes the total amount of heat produced by the CCeCV charging
process, which could be measured by calorimetric devices.
Based on constraints expressed in formulas (3)e(5), this work
intends to yield achievable values for these variables to best satisfy
the optimization target as denoted in Eq. (2). Genetic algorithm
(GA) was adopted in this work, taking the advantages of its ability
to resolve global optimal solutions, which can affirm the shortest
charging time on the premise of easing the constraints imposed by
the charging conditions. In principle, satisfying these constraints
should imply a higher efficiency and less harm to the battery's
performance by the charging protocol.
2.4. SOC and heat generation constraints
 
Qd Ic0 tc0 þ Qc0 Qc
tc ¼  (11)
Qd0 Ic Ic
where the capacity discharged Qd, capacity restored Qc, ohmic
resistance RU, polarization resistance Rp, polarization voltage Up, CC
charging terminal voltage Uc, CC charging time tc, CC rate Ic, and the
extent of polarization t are used to describe the dynamic electro-
chemical process based on an ECM. At a certain state of aging, the
parameters Uc, Up, Rp, RU, Qc, Qd, tc, Ic and t are deformed as
Uc0 ; Up0 ; R0p ; R0U ; Qc0 ; Qd0 ; tc0 ; Ic0 and t0 . For those interested in the
modeling approach, please refer to Ref. [12] for the details. The
following variables: Up, Qc, Up0 ; and Qc0 can be ignored on the
premise of no polarization from 0% SOC charging, Eqs. (10) and (11)
are thus simplified as

In this VC charging strategy, SOC can be calculated using current    

integration method in time domain as follows:   1 1
Uc0 tc0 ¼ Uc ðtc Þ þ Ic Rp exp  tc  Ic0 R0p exp  0 tc0
t t
Z

tf
0 0 0
 
iðtÞdt þ Ic Rp þ RU  Ic Rp þ RU (12)
Qc ti
SOCtf ¼ ¼ (6)
Qd Qd

where Qc represents the capacity returned during the charging Qd Ic0 0

t¼ t (13)
process, from t ¼ ti to tf, and Qd the actual capacity discharged. Qd0 Ic c
According to Eqs. (1) and (6), Eq. (3) can be rewritten as
In the VC protocol, if I was accepted at a different SOH, instead of
a h

 i CC Ic0 ; Uc0 should be deformed as U0 in Eq. (12), and the battery
btf  1 exp btf  ðbti  1Þexpðbti Þ ¼ SOCEOC
Qd b 2 voltage response can be expressed as
(7)
   
The temperature in the cell may rise because of Joules heating tc t 0  ti0
U 0 ðt 0 Þ ¼ Uc ðtc Þ þ Ic Rp exp   iðt 0 ÞR0p exp 
from the resistive effect, depicting the energy dissipated to over- t t0

  
come the resistance from charge and mass transfers [11]. The heat q 0 0 0
þ iðt Þ Rp þ RU  Ic Rp þ RU (14)
generated from the ohmic resistance (RU) is expressed approxi-
mately as
where t0 and ti0 represent VC charging time and starting time,
Ztf respectively.
q¼ i2 ðtÞdt$RU (8) The relationship between t0 and tc can be established with the
same SOC as
ti

Eq. (4) can be expressed by combining Eqs. (1) and (8) as follows Z t0
iðt 0 Þdt 0
  Ic tc ti0
a2 1

 SOC ¼ ¼ (15)
tf2  2 2btf  1 exp 2btf Qd Qd0
2b b
   (9)
2 1 According to Eq. (1), formulas (14) and (15) can be further
 ti  2 ð2bti  1Þ expð2bti Þ RU  qCCeCV
b expressed as

Relative to the variables SOC and q, the U's functional expression  

is more difficult because of the polarization effect in the LIB. tc
U 0 ðt 0 Þ ¼Uc ðtc Þ þ Ic Rp exp   at 0 expðbt 0 ÞR0p
t
 

t 0  ti0 0 0 0 0 (16)
2.5. Voltage constraint  exp  þ at expðbt Þ R þ R U
t0 p
 
In our recent work [12], we used a transformation of CC charging  Ic Rp þ RU
profiles to quantify the capacity fade in the LIBs and derived a time-
based SOH estimation model. In this model, the battery voltage !
response in the charging profiles at different stages of SOH can be Qd a0  
expressed as tc ¼ 0 ðb0 t 0  1Þexpðb0 t 0 Þ   b0 ti0
Qd Ic b02
    
    1  1 exp b0 ti0 (17)
Uc0 tc0 ¼ Uc ðtc Þ þ Up þ Ic Rp exp  tc
t

  
 where a0 and b0 correspond to a and b respectively in Eq. (1) but at a
1 0 (10)
 Up þ Ic Rp exp  0 tc þ Ic0 R0p þ R0U
0 0 0
different age.
t
  Particularly, if Uc(tc) and U0 (t0 ) were obtained at the same age of
 Ic Rp þ RU
the cell, e.g. at 100% SOH, Eqs. (16) and (17) can be rewritten as
 Z. Guo et al. / Journal of Power Sources 274 (2015) 957e964
   
tc t  ti
UðtÞ ¼ Uc ðtc Þ þ Ic Rp exp   at expðbtÞRp exp 
t t
 
þ ðat expðbtÞ  Ic Þ Rp þ RU
a
tc ¼ ððbt  1ÞexpðbtÞ  ðbti  1Þexpðbti ÞÞ
Ic b2
When t ¼ tf, the voltage constraint in Eq. (5) can be elaborated as
   
tc
 t  ti
Uc ðtc Þ þ Ic Rp exp   atf exp btf Rp exp  f
t t


  
þ atf exp btf  Ic Rp þ RU ¼ VEOC
a


 
tc ¼ btf  1 exp btf  ðbti  1Þexpðbti Þ
Ic b 2
To this end, the constraints (3)e(5) are now transformed to
formulas (7), (9), (20) and (21), making the functional variables (i.e.
a, b, ti, and tf) in the optimum charging protocol more feasible to be
determined by GA. Among these constraints, Uc(tc) can be acquired
first during CC (Ic) charging, and the parameters (RU, Rp, and t) can
be subsequently identified accurately using numerical regression.
3. Experimental
The framework outlining the experimental work is as follows:
(1) Use a type of commercial cells to illustrate the concept and
derive relevant information for validation. (2) Conduct a series of
tests to obtain data for deriving a cell performance model and
charging protocol for further evaluations and comparisons. (3)
Perform charging and cycle aging experiments to verify concept
and evaluate impacts.
Three 2.2 Ah {LiCoO2 þ LiNixMnyCozO2} composite cathode-
based LS-18650 LIB cells were used in this work, denoted as
#1e3, for testing and evaluation using an Arbin BT-2000 battery
cycler. Cell #1 was used to acquire the characteristic charging
curves for deriving the UVP and the input parameters for the ECM
simulations. The typical CCeCV protocol with a specific rate (i.e.
0.2C, 0.5C, 1C, 2C, or 3C) in the CC step was used for charging. Each
rate used in the CC step shall determine a corresponding charging
curve for analysis and model development. Cells #2 and #3 were
evaluated to determine the performance variations of the cells to
verify if the UVP is sufficiently universal. The cells were quite
consistent according to the test results. As such, the condition of
100% SOH was considered invariable, based on the experimental
results of cell voltage, charging duration, and heat generated.
Subsequently, all three cells were cycle-aged to 80% SOH (i.e. a 20%
capacity fade) using three specific protocols. In the cycle aging tests,
the discharge regime for all three was CC ¼ 1C and VEOD ¼ 3.0 V. For
comparison of charging characteristics, three different charge re-
gimes were used. Cell #1 was recharged using CC ¼ 0.5C, Cell #2
CC ¼ 2C, by the CCeCV protocol, where CV ¼ 4.2 V with IEOC ¼ C/20.
It is worth mentioning that Cell #2 would end up with a charging
time of about 1 h, close to that used as a constraint in the UVP
protocol, which was used by Cell #3. The UVP simulated from Cell
#1 at SOH ¼ 100% could be applied to Cell #3 directly. However, the
tester used in this work would not allow such a UVP function-based
commend in the test schedule. Instead, a series of multiple incre-
mental voltage or current steps (with 1 s interval) was used in the
test schedules to mimic the UVP. The experiment with Cell #3 was
thus conducted as follows: (1) Using the UVP derived from Cell #1, a
961
VCP correspondence was simulated for Cell #1. (2) Using the VCP to
charge Cell #3 to yield a cell voltage vs. time profile for comparison
with the UVP from Cell #1, to understand the effect of cell vari-
ability and its influence on VCP (assuming conversion of UVP to VCP
is independent of cell variability). (3) Applying the UVP derived
(18)
from Cell #1 to Cell #3 in the cycle aging tests to record VCPs at
different SOHs. To assess the charging efficiency for comparison,
(19) the integral energy obtained from multiplying the capacity and
voltage for the charge and discharge regimes respectively was used
in the calculation of charging efficiency. The variation of the
charging efficiency as a function of SOH was used in the comparison
between conventional CCeCV (Cell #2) and UVP (Cell #3) protocols
to assess the impacts on cell performance, particularly the cycle life.
4. Results
(20)
4.1. Cell performance model at 100% SOH
(21)
Five voltage vs. time charging curves in the CC step for Cell #1 at
SOH ¼ 100%, in the current range from 0.2C to 3C, are shown in
Fig. 1(a). These CC charging curves were used to obtain the corre-
sponding Uc(tc) functions using a nonlinear least squares method.
Subsequently, using Eq. (12) the following simulation results using:
(1) Ic0 ¼ 0.5C and Ic ¼ 0.2C, (2) Ic0 ¼ 1C and Ic ¼ 0.2C or 0.5C, (3)
Ic0 ¼ 2C and Ic ¼ 0.2C, 0.5C, or 1C, and (4) Ic0 ¼ 3C and Ic ¼ 0.2C, 0.5C,
1C, or 2C, were conducted to obtain the minimum sum of root mean
square errors (RMSEs) between the measured and estimated
voltage values in the charging curves. In the derivation, ðUc0 ; tc0 Þ was
updated according to Ic0 variations from (Uc, tc), and three param-
eters (RU ¼ 0.062 U, Rp ¼ 0.125 U, and t ¼ 1.542) were determined
ultimately in the iteration processes of fitting.
Eventually, only four variables (i.e. a, b, ti, and tf) were needed in
the optimization as illustrated by formulas (1), (2), (7), (9), (20) and
(21). The GA was used to obtain an optimal value for the above
variables, in which the population size was set to 20 and generation
2000. In particular, certain safety constraints either provided by the
manufacturer or derived from common trade practice were
included in the design of charging protocols (e.g. the maximum
charging current Imax  3C and upper cut-off voltage Umax  4.2 V
were observed at all time). After iterations, the variables were
determined as follows: a ¼ 68.80, b ¼ 5.50, ti ¼ 0.04 h, and
tf ¼ 1.04 h.
4.2. Case studies at various SOHs
As Cell #1 faded through cycle aging, resulting in different SOHs,
the complexity to derive suitable parameters for the entire cycle life
becomes labor and resource intensive, time consuming and
inconvenient in both CC profile data collection and analysis. To
simplify the process while managing to address the dependence on
SOH, as described in Eqs. (10) and (11), an effective approach as
reported in Ref. [12] was adopted hereto estimate Qd0 =Qd ; R0U ; R0p ,
and t0 using the pre-determined RU, Rp, and t. This approach used a
series of CC profiles in the charging regime through the cycle aging
of Cell #1 for illustrating how the process could be simplified.
Adopting the capacity-based convention for SOH, denoted as
Qd0 =Qd , the approach as described in Ref. [12] is convenient and
practical to quantify SOH by using an adaptive transformation of CC
charging curves at any point in life to a time-based parameter that
can be used to specify SOH. For those interested in the detail of the
time-based transformation to derive SOH should refer to Ref. [12],
and it would not be repeated here. Parameterization of the model in
this work at various SOHs was realized by a nonlinear least squares
fit of the time-based SOH parameters. The errors in the SOH esti-
mation between the estimated and experimental values (DSOH)
962 Z. Guo et al. / Journal of Power Sources 274 (2015) 957e964
were <2% throughout the entire cycle life, as reported in Ref. [12].
The parameterization of R0U ; R0p , and 1/t0 from 100% to 80% SOH is
shown in Fig. 3(a).
In the estimation of variables for each SOH case, the GA was used
to derive the optimal current profile in Eq. (1) and the reasonable
time in Eq. (2), which were denoted as a0 , b0 , ti0 and tf0 . In practical
applications, according to the pre-determined ti and tf, the charging
time ðtf0  ti0 Þ  (1.04e0.04 h) was considered as a constraint here,
irrelevant to the current levels, whereas the heat generation was
negligible and neglected (based on charging efficiency). Further-
more, the pre-determined four variables for 100% SOH were used
for the initialization of the GAs, which improved the efficiency of
GA to handle the enormous amount of data produced in the cycle
aging tests. The variable estimation results for various SOHs are
shown in Fig. 3(b).
5. Discussion
5.1. The universal voltage protocol (UVP)
Fig. 4 shows (a) the VCP, (b) cell voltage vs. charging time, (c) cell
voltage vs. SOC, and (d) SOC vs. time profiles for the entire service
life of a LIB. For better visualization, in Fig. 4(a) the interval (DSOH)
between two subsequent current vs. time curves was set to 2% in
the presentation with the t ¼ (tf  ti) scale, whereas the initial time
was set to ti ¼ 0 for all cases with the SOH dependence, so the
current level at t ¼ ti in Eq. (1) could be aligned for comparison.
Similar styles of presentation are used in the other three illustra-
tions. As the trend of VCP in Fig. 4(a) shows, while the cell fades, the
maximum current shall decrease to accommodate increasing cell
impedance, which could enjoy the benefit of less heat generation
during charging. Despite the SOH was varying, the cell voltage vs.
charging time curves (Fig. 4(b)) show remarkable similarity in
shape. The difference in the voltages between two adjacent profiles
is merely within 0.015 V through the entire charging duration. The
resemblance among the cell voltage vs. SOC curves implies that the
charging protocols are conforming to the impedance increase due
to capacity fade in the aging, a consequence of ‘kinetic voltage fade’
associated with higher polarization imposed by the increasing
impedance.
According to basic electric circuit theory, the voltage- and
current-driven charging protocols should have the same perfor-
mance and result in a reliable charging operation. For a battery
system, voltage protection is critical to prevent overcharging or
overdischarging. The cell voltage vs. time and cell voltage vs. SOC
profiles for specific cell chemistry shall serve the purpose to control
cell charging process and maintaining a consistent characteristic
charging profile commensurate with the reaction kinetics as the
SOH varies. Such a consistency revealed in Fig. 4(b)e(d) allows us to
Fig. 3. (a) The characteristic parameters changes for SOHs, and (b) functional variables changes for SOHs, along with those estimated from the reciprocal charging time.
assert that this voltage-driven charging protocol is universal, and
consistent charging results can be retained throughout a battery's
service life to enhance reliability and safety. An immediate benefit
of this practice is that the UVP only requires the parameters being
acquired and derived in the beginning of life from a fresh cell, and
the UVP is rather independent of aging condition and cell vari-
ability. This unique aspect is convenient and practical for real ap-
plications. It is very different from current-based approaches.
The voltage curves, comprise both voltage vs. time and voltage
vs. SOC information for specific cell chemistry, have the ‘uniform’
characteristics in accordance with 100% SOH one. So, the voltage-
driven protocol, denoted as ‘UVP’ here, only requires the test re-
sults from a fresh cell, independent of aging and cell variability.
5.2. Impacts from cell variability and SOH
Comparing the cell voltage vs. time curve from Cell #3 could
allow us to assess the degree of variations and inconsistency in
applying UVP to other cells in the batch in the charging processes
and at various SOHs. Fig. 5(a) shows the comparison between the
cell voltage vs. time curve of Cell #3 and UVP from Cell #1. Small
deviations were found around 0.15 h, where current levels near the
maximum. From 0.4 h to 0.7 h the deviation became more visible.
Although it is difficult to verify the origin of such differences, we
incline to believe that the VCP should impose different polarization
effects to Cells #1 and #3. Likely, the VCP on Cell #1 created more
polarization than on Cell #3. This disparity is however not a great
concern, because the deviation reduces gradually as the current
decreases. In real applications if a true UVP were used, the differ-
ences in the polarization effects shall induce variations in the VCP
in each cell, which could cause some small variations in the
coulombic efficiency, but should never cause overcharging if Li
plating were not present. Fig. 5(b) shows the resulting VCPs from
using the same UVP at different SOHs (in 5% DSOH intervals) with
Cell #3. The result illustrates a consistent descending trend in ac-
commodating capacity fade and impedance change in cycle aging
to achieve optimal charging. In all accounts, the SOCEOCs were all
>98%, indicating the UVP works well as intended.
5.3. Impacts on cell performance
Additional characterizations and assessments were conducted
to understand the benefits and capabilities of this UVP approach in
minimizing degradation of the battery performance and prolonging
the service life of the battery. A comparative study on the impacts
from charging protocols, i.e. the CCeCV with Cell #2 vs. the UVP
with Cell #3, was conducted in this work. Under the cycle aging
with the same charging time (1 h or so) and 1C discharging regime,
the resulting SOH vs. cycle number is illustrated in Fig. 6(a) and
 Z. Guo et al. / Journal of Power Sources 274 (2015) 957e964 963

Fig. 4. (a) Charging current vs. time as a function of SOH, (b) charging curves as a function of SOH, (c) cell voltage vs. SOC as a function of SOH, and (d) SOC vs. time as a function of
SOH.

Fig. 5. (a) Charging curves comparison between the simulated (Cell #1) and the experimental results obtained from Cell #3 using VCP, (b) charging current vs. time curves at various
SOHs for Cell #3 using UVP in the cycle aging.

Fig. 6. (a) Charge retention as a function of cycle number for Cell #2 and #3 using different charging protocols, and (b) charging efficiency as a function of SOH for Cell #2 and #3.
964 Z. Guo et al. / Journal of Power Sources 274 (2015) 957e964
charging efficiency vs. SOH in Fig. 6(b). To reach 80% SOH, it took
100 cycles for Cell #2, yet 370 cycles for Cell #3, which shows the
merit of prolonging cell's cycle life with the UVP charging. The rapid
decline of capacity with cycle number in Cell #2 reveals that the
cell's performance degraded severely, likely due to the result of Li
plating under repeatedly high-rate charging at 2C. In contrast, the
application of UVP in Cell #3 reduced such an effect and resulted in
a much improved cycle life. Although we could not conduct a
postmortem analysis to verify if Li plating were occurring, the trend
of fading is similar to other cases we knew that had such fading
events verified by postmortem analyses.
The fluctuations in SOH on Cell #3 during cycle aging, as shown
in Fig. 6(a), appeared more profound in magnitude than those in
Cell #2. Although the major difference between the two experi-
ments was charging protocols, it is unlikely that the fluctuations
were created by cell variability, instrumental artifact, or control
circuit accuracy. Since the SOH is a direct measurement of capacity
fluctuations in the cell through cycle aging, as a time-based cutoff
charging protocol with UVP, it is likely that the tapered charging
near the EOC may become more fluctuated than in CCeCV and
from cycle to cycle. It is conceivable that there is a finite loss of
charge to parasitic reactions. This is an attribute to the common
‘imperfectness’ in the coulombic efficiency. In the tapered charge,
some of the current could be used in the makeup of this charge
loss (noted as Qr here). This Qr is a tangible contribution to not
only the coulombic efficiency but also the overall capacity fade
and SOH. In the CV step, which serves as a mean to tapered
charging in the CCeCV protocol, Qr should be gradual (due to
increased polarization effects that reduce charging efficiency)
from cycle to cycle, with small fluctuations often caused by
instrumentation control. In contrast, with UVP, tapered charging
also plays a role when the cell is gradually approaching a terminal
cutoff voltage of a specific SOC (ideally 100%). However, the time-
based cutoff does not warrant a true tapered charge with minimal
Qr; thus, it renders the tapered charging less effective in making
up a minimum Qr, which may lead to ‘undercharging.’ Interest-
ingly, the ‘undercharging’ could provide an opportunity for the
subsequent charging to increase its charging efficiency. This in-
cremental enhancement could then reach an optimal recharge in a
few cycles, in which the maximum capacity is exhibited. After that,
the charging efficiency shall decrease again due to the ‘under-
charging’ phenomenon. Such small incremental changes over a
number of cycles make the SOH varies in a cyclic manner, as
shown in Fig. 6(a).
Fig. 6(b) shows the improvement in charging efficiency with the
UVP charging method throughout the cycle aging from fresh cell to
SOH ¼ 80%. The charging efficiency in Cell #2, which employed
CCeCV protocol declined with SOH during the cycle aging. In
contrast, the charging efficiency remains rather constant for Cell
#3. Maintaining consistent charging efficiency prolongs cycle life.
There are additional issues with the UVP charging. One of them
is the uncertainty of the SOC at the EOD, which leads to a deviation
from 0% SOC and residual unleashed charge in each cycle. This
leaves an uncertainty in the initial state for the UVP charging
control. If the cell were not fully discharged (i.e. SOC > 0), the initial
SOC ought to be estimated accurately before commencing the UVP
charging. Techniques such as Kalman filtering could be applied
based on the voltage vs. SOC correspondence. Once an accurate SOC
estimate was obtained, the modification of the initial condition for
the UVP would be amended inline and applied to the charging
regime and the corresponding charging time could be reset
precisely.
Although the results demonstrated here are for single cells, the
same approach can be applied to parallel-cell or string systems
where the inconsistency among the parallel units may exist.
Because the charging protocol is controlled by the UVP, a parallel
configuration does not introduce any complexity in managing ter-
minal voltage or charging time, while the VCP acts conformably to
the parallel circuit requirement.
6. Conclusion
Here we proposed a universal voltage protocol (UVP) for opti-
mum fast charging strategy, which could not be resolved by con-
ventional CCeCV or floating charging methods. The approach is
also fundamentally different from prior varying current techniques.
In this UVP approach, an electrical equivalent circuit model (ECM)
was employed to derive the UVP using battery characteristic pa-
rameters: RU, Rp, and t in the ECM and charging time as a constraint
in the model. This UVP charging can be applied to recharging cells
of the same design without considering cycle or calendar aging.
Alternatively, a variation of the UVP can be made with the deriva-
tion of the corresponding varying current profile (VCP) deduced
from the ECM using a generic algorithm to optimize the variables
for a nonlinear VCP. This VCP can accommodate cell aging to pro-
vide an adaptive VCP function, if the true capacity of the cell after
aging is properly estimated using the technique reported in our
prior work. This SOH estimation was based on a time-variant fitting
of CC charging curves against the initial voltage vs. time curve of a
fresh cell. The time variant shall provide the information of degree
of aging of the cell; thus, its capacity at a specific SOH. This accurate
capacity estimation as a function of SOH shall facilitate the
correction of the VCP through its service life. Through experimental
validation, this UVP/VCP approach is attractive for practical appli-
cations with the following advantages (1) adaptability to SOH
variations, (2) a simple UVP that is independent of aging, (3)
quantitative VCP modification according to charging time and aging
condition to yield a higher charging efficiency, overvoltage pre-
vention, and easy implementation of fast charging.
Acknowledgments
This work is funded by Tsinghua National Laboratory for Infor-
mation Science and Technology (TNList) Cross-discipline Founda-
tion, and NSFC (Grant No. 61021063).
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